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New Concepts in Polymer Science

Polymers for Packaging and Containers


in Food Industry

New Concepts in Polymer Science


Previous titles in this book series:
Low-Temperature Behaviour of Elastomers
M.F. Bukhina and S.K. Kurlyand

Modern Polymer Flame Retardancy


S.M. Lomakin and G.E. Zaikov

Radiation Chemistry of Biopolymers


G.E. Zaikov and V.A. Sharpatyi

Polymeric Biomaterials.
Part I. Polymer Implants
M.I. Shtilman

Polybutilene Therephthalate (PBT),


Synthesis and Properties
M.A. Mikitaev, T.A. Borukaev.
Edited by G.E. Zaikov
Photodegradation and Light Stabilization of
Heterochain Polymers
F. Niyazi, I.V. Savenkova and G.E. Zaikov
Elementorganic Monomers: Technology,
Properties, Applications
L.M. Khananashvili, O.V. Mukbaniani
and G.E. Zaikov
The Structural Stabilization of Polymers:
Fractal Models
G.V. Kozlov and G.E. Zaikov

Biodegradation and Durability of


Materials under the Effect of Microorganisms
S.A. Semenov, K.Z Gumargalieva
and G.E. Zaikov
Fire Resistant and Thermally Stable Materials Derived from Chlorinated Polyethylene
A.A. Donskoi, M.A. Shashkina and G.E.
Zaikov
Polymers and Polymeric Materials
for Fiber and Gradient Optics
N. Lekishvili, L. Nadareishvili,
G. Zaikov and L. Khananashvili

Thermal Oxidation of Polymer Blends. The


Role of Structure
L.S. Shibryaeva, A.A. Popov and G.E. Zaikov

Polymers Derived from Isobutylene.


Synthesis, Properties, Application
Yu.A. Sangalov, K.S. Minsker and G.E.
Zaikov

Biocide Guanidine Containing Polymers:


Synthesis, Structure and Properties
N.A. Sivov

Ecological Aspects of Polymer


Flame Retardancy
S.M. Lomakin and G.E. Zaikov

Active Sites of Polymerization.


Multiplicity: Stereospecific and Kinetic
Heterogeneity
Y.B. Monakov, N.N. Sigaeva and N. Urazbaev

Molecular Dynamics of Additives in Polymers


A.L. Kovarski

Stationary and Non-Stationary Kinetics


of the Photoinitiated Polymerization
Yu.G. Medvedevskikh, A.R. Kytsya,
L.I. Bazylyak, A.A. Turovsky and G.E. Zaikov
Thermal Stability of Engineering
Heterochain Thermoresistant Polymers
E.V. Kalugina, K.Z. Gumargalieva
and G.E. Zaikov

Structure and Properties of


Conducting Polymer Composites
V.E. Gul'
Interaction of Polymers with
Bioactive and Corrosive Media
A.L. Iordanskii, T.E. Rudakova and G.E.
Zaikov
Immobilization on Polymers
M.I. Shtilman

The Concept of Micellar-Sponge


Nanophases in Chemical Physics of Polymers
Yu.A. Mikheev, G.E. Zaikov

Radiation Chemistry of Polymers


V.S. Ivanov

Structure of the Polymer Amorphous State


G.V. Kozlov and G.E. Zaikov

Reactive Oligomers
S.G. Entelis, V.V. Evreinov and A.I. Kuzaev

The Statistical Nature of Strength and Lifetime in Polymer Films and Fibers
B. Tsoi, E.M. Kartashov and V.V. Shevelev

Diffusion of Electrolytes in Polymers


G.E. Zaikov, A.L. Iordanskii and V.S. Markin

Cyclolinear Organosilicon Copolymers:


Synthesis, Properties, Application
O.V. Mukbaniani and G.E. Zaikov

Polymeric Composites
R.B. Seymour

Chemical Physics of Polymer


Degradation and Stabilization
N.M Emanuel and A.L. Buchachenko

New Concepts in Polymer Science

Polymers for Packaging


and Containers
in Food Industry
L.A. Sukhareva, O.A. Legonkova and
V.S. Yakovlev.
Edited by G.E. Zaikov

LEIDEN BOSTON - 2008

Printed and bound In The Netherlands

ISSN 0928-1584
ISBN 978 90 04 16143 6
Copyright 2008 by Koninklijke Brill NV, Leiden, The Netherlands.
Koninklijke Brill NV incorporates the imprints Brill, Hotei Publishing,
IDC Publishers, Martinus Nijhoff Publishers and VSP.
All rights reserved. No part of this publication may be reproduced, translated, stored in a
retrieval system, or transmitted in any form or by any means, electronic, mechanical,
photocopying, recording or otherwise, without prior written permission from the publisher.
Authorization to photocopy items for internal or personal use is granted by Koninklijke Brill NV
provided that the appropriate fees are paid directly to The Copyright Clearance Center,
222 Rosewood Drive, Suite 910, Danvers, MA 01923, USA.
Fees are subject to change.

Contents

Introduction
1 Methods and technology of preserving the nutritive value of food
1.1 The nutritive value of foodstuffs
1.2 Methods and technology of preserving food products and raw materials
1.3 Technology of preserving the quality of foodstuffs in manufacturing,
transportation and sales
1.4 Application of chemical preservatives in food industry
1.4.1 General information on chemical food preservatives
1.4.2 Mechanism of action of chemical preservatives
1.4.3 Characteristics and application of chemical preservatives
1.4.4 Methods for identification of preservatives
1.4.5 Fat antioxidants
1.4.6 Effect of oxidation on the food value of fats
1.4.7 Inhibition of autooxidation processes
1.4.8 Characteristics and application of antioxidants and synergists
1.4.9 Comparative efficiency, methods of treatment and admissible
concentrations of antioxidants
1.4.10 Methods for identification of antioxidants
2 Polymer packaging materials for preservation of foodstuffs
2.1 Food polymers
2.2 Hygienic characteristics of packaging materials components
2.3 Methods of packaging foodstuffs
3 Combined packaging materials using cellulose and its derivatives
3.1 Internal stresses in coatings using cellulose
3.2 Moisture-resistant packaging materials based on cellophane
3.2.1 Justification of the composition of the coating
3.2.2 Copolymer-based coatings
3.2.3 Coatings based on lacquer compositions
3.2.4 Design of heat sealed seams
3.2.5 Justification of the choice of solvent
3.2.6 Wetting of hydrated cellulose film with some organic solvents
and solutions of SVN-80 on the basis of these solvents
3.2.7 Working-out of an optimal process regime for producing
cellophane SVN-80

1
5
5
9
17
24
24
26
28
34
35
44
46
49
63
65
71
71
75
82
105
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115
118
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123
125

vi

CONTENTS

3.3 Modification of cellulose diacetate for packaging materials


3.4 Interaction of cellulose with water

127
130

4 Compositions for decorative finish and protection of packaging products


4.1 Bases of the formation of protective and decorative finish coatings
4.2 Application of aqueous dispersions of polymers for finishing products
4.3 The formation mechanism, structure and properties of finishing
packaging materials from aqueous dispersions
4.4 Characteristics of finishing packaging materials
4.5 Aqueous dispersions of polymers for finishing coatings, offset papers
and inks
4.6 Properties of finishing coatings from aqueous dispersions of acrylic
polymers
4.7 Specifics of forming coatings on paper and offprints

133
133
139

5 Technology of the development of canning containers


5.1 Purpose of canning containers
5.2 Field of application and efficiency of use
5.3 Requirements to the properties of coatings for canning containers
5.4 Coatings for protection of canning containers
5.5 Compositions based on oligomer systems
5.6 Oleo-resinous lacquers
5.7 Polyvinyl chloride-based lacquers
5.8 Oligoesters and water-base, water-soluble and water-dispersion binders
5.9 Compositions with high dry residue and ink powders
5.10 Coatings for protection of the outer surface of canning containers

181
181
183
184
186
189
191
192
193
195
196

6 Structure and properties of compositions for protection of canning


containers
6.1 Ways of improving the protective properties of coatings
6.2 Effect of the nature of the support on the structure and properties of
coatings
6.3 Structure formation in solutions of epoxyphenol compositions and
the properties of coatings
6.4 Dependence of the properties of can lacquers on the structure of
phenol-formaldehyde oligomers
6.5 Fields of application of canning containers and methods of their
modification
6.6 Structure and properties of coatings based on epoxy oligomers
6.7 Technology of producing protective polymer coatings
6.8 Specific features of forming epoxyphenol coatings for canning containers
7 Ways of increasing the protective properties of coatings for canning
containers
7.1 Coatings with enhanced adhesion to aluminium and its alloys
7.2 The role of solvent in the formation of the properties of coatings for
canning containers
7.3 Effect of the nature of epoxy oligomers on the properties of coatings
7.4 Water-base compositions for protection of canning containers
7.5 Modification of polyvinyl chloride compositions by thermoplastics

145
151
154
158
177

201
201
202
203
208
212
216
219
222
231
231
232
236
237
240

CONTENTS

Effect of the structure of the block copolymer chain on the properties


of coatings
7.7 Development of the method for improving the protective properties
of polyvinyl chloride compositions by modification with block copolymers
7.8 Studies of the relaxation properties of coatings from polyvinyl chloride
compositions modified by thermoplastics
7.9 Modified perchlorovinyl coatings with increased shelf-life

vii

7.6

8 Ways of modifying the properties of metallized packaging materials


8.1 Purpose and fields of application
8.2 Methods of forming metallized layers on polymer materials
8.3 Protective coatings for metallized materials
8.4 Methods of modifying the structure and properties of epoxy coatings
8.5 Protective coatings from copolymers of regular structure
8.6 Combined metallized materials for dairy produce packing
8.6.1 Combined material based on polyethylene, paper and aluminium foil
8.6.2 Hermeticity of polymer packaging
8.6.3 Coextruded polyethylene films for packaging dairy produce and
their quality indices
9 Technology of forming and modifying multilayer metallized packaging
materials
9.1 Purpose and production of multilayer materials
9.2 Prospects of using metallized packaging materials
9.3 Polymer films as the base for metallization
9.4 Methods of modifying the properties of films
9.5 Structure and properties of film materials
9.6 Ways of protecting metallized packaging materials
9.7 Effect of modification on the properties of protective coatings from
epoxy compositions
9.8 Technology of producing protective coatings with improved performance
properties
9.9 Ways of thixotropic decrease of internal stresses in the formation of
coatings from polymer dispersions for finishing of packaging materials
9.10 Modification of finishing dispersions for paper and offprints by
polymer systems
9.11 Combined packaging materials with increased protective properties
9.12 Effect of pH of the medium on the specific features of structure formation
and the properties of coatings from polymer dispersions
9.13 Polyurethane chemically resistant coatings for protection of container
and packaging materials
9.14 Protective polyurethane coatings and adhesive compounds
10 Methods of developing polymer gas-selective systems for storage of fruits
and vegetables
10.1 Problems of storage of agricultural raw materials and foodstuffs
10.2 Selectively permeable polymer materials
10.3 Effect of diffusion characteristics of polymer materials on the formation
of a gas medium

241
242
246
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253
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254
258
260
264
267
267
269
272
277
277
282
284
288
290
293
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305
313
315
321
325
333
333
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viii

CONTENTS

10.4 Methods of developing an optimal gas medium and the technology of


storage
10.5 Efficiency of using polymer materials and protective coatings in
long-time storage of fruits

340
340

11 Structure and properties of oligomer compositions for protection of transport


containers
345
11.1 Corrosion resistance of coatings for transport containers
345
11.2 Structural conversions in hardening of thermosetting oligomers
346
11.3 Formation kinetics of coatings from polymerization oligomers
351
11.4 Causes of internal stresses in formation of coatings
357
11.5 Effect of the nature of hardener and initiator on the formation and
properties of coatings for transport containers
366
11.6 Biodeterioration of container/packaging materials
381
11.7 Effect of the polymerization initiation method on the formation and
properties of coatings for transport containers
387
11.8 Studies of the possibility of using stabilized radicals in protective coatings 395
12 Biochemically stable coatings for protection of transport containers
12.1 Coatings based on Ftorlon copolymers
12.2 Structure of modified Ftorlon coatings
12.3 Coatings based on modified and ladder polyphenyl sesquioxanes
12.4 Photohardenable epoxy acrylates for protection of transport containers
12.5 Physicochemical bases of developing photohardenable coatings
12.6 Photochemical processes and structural transformations in formation
of coatings under the action of ultraviolet light
12.7 Properties of epoxy acrylate coatings for transport containers
12.8 Biocidal coatings based on styromal

401
401
402
403
405
406

13 Technology of the protection of large-tonnage foodstuff containers


13.1.1 Methods of protecting storage tanks for potable 96% ethyl alcohol
13.1.2 Objects and methods of studies
13.1.3 Results of studies
13.1.4 Technology of anticorrosion protection of the inner surface of
ethyl alcohol storage tanks
13.2 Bactericidal wear-resistant coatings for storage and processing of grain
and grain products
13.3.1 Modified coatings of tanks for storage of vegetable oil
13.3.2 Results of tests
13.4 Food-grade coatings resistant to the action of sign-variable temperatures

431
431
432
433

14 Ecology and safety of utilization of container/packaging materials


14.1 Methods of utilization of packaging materials
14.2 Accelerated degradation of polymers by biocides
14.3 Photodegradable polymers
14.4 Modified photodegradable polymers
14.5 Principles of developing modifiers for biodegradable materials
14.6 Industrial and domestic plastics wastes
14.6.1 Secondary plastic raw materials in the public reproduction process
14.6.2 Sources and turnarounds of secondary polymer raw materials

455
455
456
456
458
462
464
464
465

410
421
425

436
440
444
448
452

CONTENTS

14.6.3 Economic assessment of secondary plastic raw materials


14.6.4 Collection and use of thermoplastic wastes from domestic
consumption sphere
14.6.5 Separation of plastic wastes from domestic garbage
14.6.6 Application of plastic wastes as fillers and additives
14.6.7 Mechanism of degradation
14.6.8 Energy efficiency of incineration of plastic wastes
14.7 Secondary raw materials based on packaging material wastes
14.8 Use of secondary energy resources
14.9 Economic and ecological aspects of utilization of secondary raw materials
14.10 Self-degrading polymer materials
15 Packaging of meat and meat products
15.1 Range of single-layer packaging materials in meat packaging
15.2 Combined film materials
15.3 Modern trends in the development of chilled meat packaging technology
15.4 Methods and equipment for packaging of meat and meat products
15.5 Active packaging technology

ix

468
470
473
475
477
479
480
480
482
485
491
492
498
503
508
512

Conclusion

517

References

519

CONTENTS

Introduction
Development of the concept of long-term food storage is an independent field of scientific
and applied research using polymers of various chemical compositions and structures.
It includes elaboration of technology of storing food products and food staples using
advanced packaging materials. Their development is based on studies of temporal regularities of the quality of products depending on chemical composition, properties and structure. External factors are to be considered, too; they include conditions and terms of storage,
air temperature and humidity, biocide properties of container/packaging materials, quality
assessment criteria in turning out/accepting products and in long-time storage.
Based on the studies of the dynamics of the process, analysis of numerous results of
research, it became possible to predict the regularities in the change of quality and terms of
product storage, as well as the criteria of the impact of containers and packaging on them.
Food products are a complex object; various physico-chemical processes occur in
them in production and storage, thus changing their properties and nutritive value. Such
basic ingredients as proteins, lipids, carbohydrates are polyfunctional compounds, which
are involved in diverse intra- and intercellular interactions.
Despite the diversity and complexity of food products, they are an integral biological
system with its characteristic features. The basis of the organization of biologically active
food systems are variability, preservation and stability.
A determining factor in the development of the scientific approach to storage of food
products is the variability of the properties, and storage appears to be the unity of changes
and preservation, variability and stability.
The properties of food products and their changes in storage should be considered
under conditions of the multi-factor relationship of internal and external effects.
Stability of food products in storage is characterized by processes, which lead to a decrease of the consumer properties of foodstuffs. The directedness of these processes is determined by internal factors and initial properties of a product: the peculiarities of chemical
composition, ratio of the main components, activity of the enzyme systems, occurrence of
natural antioxidants. This system is affected by external factors capable of inhibiting or activating the active processes in food products. There is an exchange between the medium
and the product an exchange of mass, energy and information.
A system becomes stable and reliable when it is capable of reacting to the influence
of an external medium by changing it in accordance with its inherent properties. Food products, which are biological systems, do not passively obey the influence of the external medium but actively counteract it, following its own processes due to its potentialities, its
resistance to the effects of individual factors. Therefore, the ability of food products to react
to an external effect is considered to be an essential factor of self-preservation.

INTRODUCTION

Of great importance in long-time storage of food products are polymers for containers
and packaging. For an open system, a container is a barrier between a product and external
factors. The requirements to containers are dictated by the properties of a product and the
character of its mass exchange with the external medium.
In products suitable for long-time storage, biological (microbial, enzymic) processes
are completely or almost completely excluded. Products with low moisture content (not
higher than 10%) can be attributed to such products. Products with average (10 to 40%) and
high (over 40%) moisture content are capable of retaining their properties for a rather limited period of time. Preservation (sterilization, freezing, sublimation etc.) makes it possible
to considerably increase their storage time. Therefore, products suitable for long-time
storage are those with low moisture content or preserved in various ways.
The basis of long-time storage of food products is the maximum preservation of consumer properties by regulating the initial-quality change as a result of product ageing, effects of external factors, choice of containers and packaging materials.
The main processes in food products in long-time storage, which govern the guarantee
storage times, are as follows:
for products with low moisture content: exchange of moisture with the external medium and the oxidative process;
for frozen meat: heat exchange and oxidation reactions;
for sterilized preserves: changes in the protein and lipid composition as well as interaction of the product with containers metal.
Of great importance is the development of container/packaging materials for storage
and transportation of high-calorie foodstuffs under extreme conditions. They are manufactured for persons whose activity is related to prolonged physical and neuro-emotional
stresses under unfavourable conditions.
The assortment of these foodstuffs comprises dairy, meat, fish, fruit-and-vegetable and
other products, preserved by methods of thermal sterilization, sublimation drying, partial
dehydration, including:
dairy products sources of readily assimilable calcium, complete protein and fat.
They include milk beverages and curd products of sublimation drying, with added coffee,
cocoa, nuts, sea-buckthorn oil; puree from dried apricots, cranberry etc.;
sublimation-dried sour-milk products providing normalization of intestinal microflora, which is especially important in long-term consumption of preserved food;
high-fat sterilized milk preserves, including cheeses, sterilized curd products, which
are distinguished by a high content of readily assimilable protein, optimal calcium to phosphorus ratio, increased content of potassium, high energy value;
fish products (preserves and products of sublimation drying): sources of complete
readily assimilable protein, fats with a high content of polyunsaturated fatty acids, oilsoluble vitamins, major nutrients and trace elements;
meat and meat-and-cereal products (preserves, lunch packs of sublimation drying):
sources of complete protein with a balanced amino acid content owing to a combination of
animal and plant protein, minerals, as well as fats with a sufficient amount of polyunsaturated fatty acids and oil-soluble vitamins in their composition;
fruit-and-vegetable products (fruit concentrates, vegetable side dishes, juices, kissels
and compotes of sublimation drying): sources of readily assimilable carbohydrates, minerals (potassium, trace elements), vitamins, pectins, organic acids;
confectionary products distinguished by a high nutritive value at a minimum weight
and volume;

INTRODUCTION

dehydrated beverages (tea, coffee) with readily assimilable carbohydrates added.


Ready-to-eat products need minimum preparation, are portioned and are convenient
to use directly from the packaging container.
Lately, an important role is allotted to the biological safety of products, which is related to the consumption of food produced from genetically modified plants. Only in the recent
years, the global acreage of transgenic crops, such as soy, maize, tomatoes and potatoes increased more than 20-fold. Food products from them are already supplied to the table of
American and Russian consumers.
Norms and methods for the integrated assessment of the safety of genetically modified
sources of food are intensively worked out at present. Much attention is also given to the
development of advanced containers and packaging materials.
Principles of creating active packaging for food production have been proposed. Traditional basic qualities of food packaging are usually related to its inertness due to the intrinsic barrier properties of the polymer matrix. At present, the functions of packaging are
much broader. The quality of a packaging is assessed by its involvement in the preservation
of the nutritive value of a product, by its activity determined by such functions as the ability
to regulate the speed and temperature of foodstuff heating in a microwave oven; to create
an optimal gas medium inside the envelope; to change directionally the intranutrient composition of a product; to introduce flavouring materials, preservatives, gas absorbents,
moisture adsorbents, antimicrobial preparations; as well as to use special coatings to improve the appearance and decorative properties of a packaging.
The purpose and functions of polymer and combined aseptic packaging have broaden.
The modern approach to packaging engineering of the 21 century is considered with
account for three directions of the development of active packaging, which, as the result of
introducing special additives, affects the quality of food products.
The first way of creating active packaging is based on the principles of forming a regulated modified gas medium using special membranes, adsorbents of oxygen, ethylene, for
instance, in storage of fruits and vegetables.
The second way is to impart a biocide activity to the packaging with respect to pathogenic microflora in the process of production and storage. The third way: in production of
food products (cheeses, uncooked dry-cured sausages) the packaging should regulate the
biochemical transformations in the product for directed regulation of its properties. In this
connection, immobilized bacterial cells and enzymes are introduced into the active
packaging.
A topical problem is to develop ecologically harmless container/packaging materials
and coatings due to the aggravated situation with providing healthy food in the right quantities. A decrease in the level of production, crumbling of structural industrial links, the unfavourable ecological situation stipulate a sharp increase of the losses of agricultural and
food products, generally lead to such negative consequences as the rise of the deficit of protein and vitamins in the food ration, pollution of food with metabolic products of pathogenic
bacteria, including with carcinogens.
Ecologically safe packaging materials are created by modifying traditional polymers
with polyfunctional additives, which perform the functions of structure formers, plasticizers, antibiotics, relaxants of internal stresses, and stabilizers. Scientific bases of creating
packaging materials for foodstuffs have been developed. Additives providing the production of materials, which are biochemically resistant to the impact of microflora and aggressive media of food productions, are introduced into the composition of their base. Methods
of regulating the processes of mass transfer and distribution of structure-forming additives

INTRODUCTION

along the thickness of the packaging materials with the aim to form an optimal structure
and operational properties have been developed.
Fundamental works have been carried out on the development of packaging materials
and coatings based on various polyolefins, ftorlons, epoxy polyesters and other polymers
of mesomorphic structure, which provide for the production of packagings with polyfunctional properties.
Special attention is given to the development of scientific principles of creating
self-degrading packaging materials with regulated service life and biodegradation upon disposal.
Valuable characteristics of these materials are determined by the necessity of combining the biocide properties with respect to foods in storage with the ability to be degraded
in soil under the action of microflora.

1
1.1

Methods and Technology


of Preserving the Nutritive
Value of Food

The nutritive value of foodstuffs

Special attention should be paid to the control of losses of food products in their processing,
storage, transportation and sale. This could not be done without scientifically grounded
rational application of polymer materials, which are used to preserve food products. In this
connection, it is necessary to consider the specific properties of both food itself and of polymers in contact with it (packaging materials, containers, various coatings).
To preserve food well, it is necessary to know which of its specific properties should
be retained until it reaches consumers table, bearing in mind the concepts healthy food
and tasty food from the viewpoint of food biochemistry. Man can not exist without food.
It provides the organism with necessary substances for growth and is a source of energy,
which is transformed into heat required for the bodily functions of the human organism.
For a long time, the only index of food value was its caloric value. Energy is constantly
consumed throughout human life to maintain the normal body temperature, for mental and
physical work. Usually, a human in normal condition should consume an amount of food,
which corresponds to energy consumption by its caloric value.
The amount of energy required for the human organism, internal consumption including, is determined in special chambers used to measure the amount of heat evolving in the
lying position, during physical or mental activities. Naturally, depending on the intensity
of work, the amount of energy evolved and, therefore, the requirement of its replenishment
at the expense of the caloric value of food would be different.
The human organism receives energy mainly due to oxidation of food. Actually, food
is not assimilated completely, and its real caloric value is slightly less than the amount
of heat evolved in its oxidation. Carbohydrates and fats burn almost completely. In oxidation of carbohydrates and proteins, the energy evolved per 1 kg is 16.8103 kJ; of fats,
37.8103 kJ.
The basis of food are proteins, fats and carbohydrates. All foods essential for health
consist of proteins, fats and carbohydrates, and also of some other components. For the
organism, it is not the same if it receives these calories by consuming carbohydrates or fats.
The latter are more difficult to assimilate, and they come to the blood flow later. Proteins
are indispensable for the organism. Apart from the fact that they replenish the energy
consumed, they provide for the restoration of expended cells and tissues and ensure the
development of the human organism at the young age.

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Food does not only deliver energy for work and is required for us to move, think, for
the heart to pump blood through the body, to maintain normal body temperature; it also provides material for the incessant regeneration of tissues and cells. The most active constituent
parts of cells and tissues, consisting of proteins, are to be regenerated first of all. Various
types of proteins can be distinguished. They perform various functions in the organism.
Proteins of connective tissues fasten muscles and bones in tendons. Proteins, of which
muscles consist, are capable of contracting and stretching, in accordance with orders from
the brain, to bring into motion organs of the human body. Proteins of the blood deliver
oxygen required for oxidation of tissues (without which the human organism is not capable
of maintaining life and performing work) and pick up the waste product, carbon dioxide.
Cutaneous coverings, hairs, mucous envelopes also consist of proteins.
Of no less importance in comparison with the above is the regulatory function of proteins. They regulate the vital processes in cells and organs. From the point of view of chemistry, these proteins catalyze and regulate chemical processes. Digestion is also one of these
processes.
Proteins in question are enzymes. Participating in the regulation of vital processes,
protein molecules are subjected to changes, as a result of which they lose their valuable
properties. Thus, it is necessary that the replacement for spent proteins come with food.
Therefore, sources of energy fats and carbohydrates are interchangeable. From the viewpoint of their energy functions, they can be replaced with proteins. Proteins themselves are
indispensable, as they are valuable for the organism not only as an energy source but also
as building material for cells and as catalysts and regulators of biochemical processes.
Therefore, the value of food products is determined not only by their caloric value but
also by the content of protein substances. The hierarchy of food products by this parameter
differs from that obtained from comparison of foodstuffs by their caloric value.
Consider the protein content in different food products consumed in this country, %:
Soy
Dry pea
Cheddar cheese
Boiled hen
Beef
Cod
Mutton
Pork
Eggs
Wheat flour

34.9
23.8
23
20.6
17
16.5
15.7
15.2
12.8
10.5

Rice
Cow milk
Potato
Cabbage
Carrot
Butter
Margarine
Marmalade
Sunflower oil
Sugar

7.6
2.8
2.0
1.8
1.2
0.6
0.3
traces
none
none

Food products can not be characterized by their caloric value alone. Despite the high
caloric values of sunflower oil and sugar, the human organism would not function in a
normal way, however large amounts of these high-calorie products are consumed. It is imperative that food of man contains fats, carbohydrates and proteins. In the human organism,
protein molecules break up to form smaller molecules, amino acids. Amino acid molecules
can be of different size and structure. Their common feature is the presence of amino and
carboxyl groups in the molecule. It has been established that amino acids required for the
vital activities of the human organism can be divided into nonessential and essential. Nonessential amino acids can be synthesized by the human organism from fragments of molecules. Essential amino acids can not be synthesized and should be obtained with food.

CHAPTER 1

Apart from proteins, fats and carbohydrates, the human organism requires vitamins.
They are essential. Certainly, vitamins can be injected or swallowed in pill form. But the
most useful method is to introduce vitamins with food. As molecules of amino acids are
fragments of large molecules of proteins, so vitamins are ready-made fragments of the most
important enzymes regulating the metabolism. Vitamins are divided into water-soluble and
fat-soluble. For example, vitamin C ascorbic acid belongs to the former. The human organism is not capable of synthesizing it, despite its comparatively simple chemical structure, probably, because the mankind has been almost always surrounded by natural sources
of vitamin C, which occurs in almost all fresh vegetables and fruits. This vitamin is present
in dill (0.15%), horseradish (0.2%), red pepper (0.25%), black currant (0.3%), winter pine
needles (0.220.28%), dry briar (15%) and in other vegetables, fruits and greens. Ascorbic acid is unstable and is easily destroyed in cooking, drying, preservation and in long-time
storage in air. Deficiency of vitamin C in food causes a severe disease, scurvy.
One of fat-soluble vitamins is widely known vitamin A, which is involved in the synthesis of rhodopsin required for good vision and is contained in fish liver oil, carrot and
other products. Vitamin A occurs mainly in products of animal origin. Its highest amount
is in beef liver and cod. The liver stores 90% of all vitamin A in the animal and human organism. Good sources of this vitamin are hens and quails eggs, butter, dairy cream and
sour cream. Though plant products contain no vitamin A, some of them (carrot, red mountain ash, sea buckthorn berries) contain a large amount of carotene up to 10 mg per 100 g
product. Under the action of carotenase in the intestines, carotene is converted to vitamin
A. Carotene is a rather unstable, readily oxidizable compound. For this reason, chopped
vegetables and greens should not be left unused for a long time, as carotene in them would
lose biological activity. Greens and vegetables should be cut immediately before a meal.
As carotene does not dissolve in water but dissolves well in fats and oil, it would be assimilated better if an edible fat is added to vegetable dishes. For instance, grated carrots could
be dressed with mayonnaise or sour cream.
The daily requirement of vitamin A is 0.50.7 mg for children aged from one up to
ten years old; 1 mg for older-age children and adults; 1.25 mg for pregnant women; 1.5 mg
for breastfeeding women.
For persons whose work is associated with a heavy load on the organs of vision, those
who work evening or night shifts or have contact with substances causing irritation of the
mucosa of the eye, the daily intake of vitamin A should be increased 1.52-fold.
Deficiency of vitamin B can cause polyneuritis. Vitamin B2 (riboflavin) is required for
normal sight. The absence or deficiency of PP (nicotinic acid) leads to a heavy disease, pellagra, and vitamin B2 contains the element cobalt required for the vital activity of the cells.
Thus, besides fats and carbohydrates, the human organism should receive with food a
set of essential amino acids, vitamins, cellulose for normal functioning of the gastrointestinal tract. But even this is not sufficient for food to be wholesome and to contain all elements required for the vital activities of the organism. The important components are salts,
which contain such elements as potassium, sodium, calcium, phosphorus, fluorine, as well
as various trace elements in small amounts. Sodium is an important constituent of the blood
and together with potassium is required for the normal functioning of the nervous system.
Human bones consist of calcium phosphate. Adenosine triphosphoric acid is a kind of an
energy storage device in the human organism. Phosphorus-containing nucleic acids code
for the program of building up and operating each cell of the organism and, therefore, the
program of constructing the entire organism, i.e., heredity. Protein molecules also include
sulfur. The absence of iodine makes impossible the normal functioning of the thyroid gland.

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Iron is a component of blood hemoglobin. Fluorine is required for the normal state of the
teeth.
However, food should be not only wholesome but also tasty and even attractive to the
eye. By its appearance and aroma, it should cause a reflectory secretion of the substances,
which contribute to the digestion and assimilation of food. Therefore, a broad diversity of
gastronomy should not be reduced to carbohydrates, fats, amino acids, vitamins and salts.
In spite of the seeming rationality of introducing a certain amount of nutrients into the organism, the human can not live on tablets or powders of even the most perfect and wellbalanced diet. It is not by chance that even at the dawn of cosmonautics, when each extra
gram of load in the spaceship significantly complicated the mission, even then cosmonauts
did not swallow powders or pills consisting of amino acids, carbohydrates, fats and other
components. The taste, smell and appearance of food is not a caprice but an essential requirement of the human organism. The diversity of taste hues can be reduced to a combination of four main gustatory properties: sour, sweet, bitter and salty. The edges of the
tongue are the most sensitive to sour taste; the base, to bitter taste, the tip, to sweet and salty
tastes. All acids have a sour taste. Cooking salt, as is known, possesses a salty taste. However, salts of most metals are not salty in taste, but bitter. In general, the relation between
the chemical structure of a substance and its taste has been investigated to date obviously
insufficiently. Peptides have a taste, which depends on which amino acids they consist of.
High-molecular-mass compounds, whose molecules are characterized by molecular-mass
magnitudes of the order of tens and hundreds of thousands are, as a rule, tasteless. This pertains to polysaccharides and polypeptides (proteins). As for the taste of amino acids, the
sweet ones are D-tryptophane, D-histidine, D-phenylalanine, L-alanine, glycine (in decreasing order). L-Tryptophane, L-phenyl alanine and the so-called L-isomers are bitter.
D-Alanine, D- and L-aspartic acids, D-glutamic acid are tasteless or have a very weak taste.
Food products are sometimes artificially flavoured, for example, to add a sweet taste.
Herewith, it is known that sugar is not the very sweet substance. Saccharine, for instance,
is 400500 times as sweet as sugar, but is not assimilated by the human organism.
Glycine (an amino acid possessing a sweet taste) is agreeable to the taste and wholesome. It is widely used in production of soups, condiments, marinades; it softens a bitter or
salty taste and eliminates an unpleasant off-flavour of some products. Glycine is present in
large amounts in fish, prawns, molluscs.
D-Tryptophane and maltol are used to enhance sweetness. Addition of maltol in the
amount of 15 ppm makes it possible to decrease the consumption of sugar by 15%.
Preparation of food boiling, broiling, roasting, fermenting, pickling, junketing etc.
is accompanied with complex chemical reactions, as the result of which a large amount of
various volatile compounds are formed. Their content in food is negligible but the flavour
of food changes depending on the ratio of these compounds in the steams.
In individual cooking, it is easier to follow the preservation of useful substances, taste,
colour and smell. It is far more difficult to bring the valuable properties of food to the consumers table, when food products are mass produced in meat-, milk- or food-packaging
plants; when these products should be preserved in the process of production, transportation
and storage in refrigerators, in the process of selling them up to the moment when the food
gets into the human organism.
Considering the problem of food preservation, one should not be abstracted from the
fact that foodstuffs are involved in the common closed process of interaction of the human
organism with the environment. The late 1970s and early 1980s witnessed the formation of
a new interdisciplinary science of food and nutrition, trophology (the Greek word

CHAPTER 1

means aliment). Trophology combines together the earlier disconnected links of the chain
and various aspects of the science of food, such as the distribution of nutrient substances in
the cell or in the organism; the mechanism of the transfer of nutrient substances along the
food chains; the role of trophological processes in the circulation of substances in the biosphere; evolution of species and evolution of the biosphere. As far as the life of each organism and the maintenance of life depend essentially on the equilibrium between the synthesis
and decomposition of nutrient substances, the biosphere can be considered as a troposphere,
and all organisms as links of the planetary food chain, a food hierarchy forming a closed
circle. The new science of trophology should combine together the earlier scattered links
of this chain.
An integrated view of the trophological process made one to approach the evaluation
of food in a new way. While it was believed earlier that the organism needed as much food
as it consumed, it was not food in general that was meant but the nutrients assimilated by
the organism amino acids, carbohydrates, fatty acids, vitamins, essential salts. All the
other components of foodstuffs were considered to be an unnecessary ballast, which complicates the bodily functions of the human organism. At present, one of the fundamental
conclusions of trophology is that, apart from the main flow of nutrients, four more flows
come to the organism. One of the most important flows is that of physiologically active substances formed in the stomach and in the intestines. The so called hormones and mediators
are implied.
If one takes account of all hormone-producing cells in the human gastrointestinal tract,
the result would be the largest endocrine gland in the human organism. This gland secretes
hormones, which control the essential metabolic functions and assimilation of nutrients.
Three other flows are formed in the gastrointestinal tract with the participation of bacterial
flora. The bacterial flora is required for the human organism and higher animals to exist.
Only the proportional ratio of all four flows creates normal conditions for the vital activities
of the organism. The so-called ballast substances, which until recently were to be withdrawn from food to make it closer to an ideal meal, are in reality also required for the
human organism. On removal of, e.g., food fibres cellulose or lignin from food, the cholesterol metabolism is disturbed, which can cause stones in the gall bladder or else a stomach or intestinal disease. Therefore, ballast-free elementary diets are applicable only in the
case of some defects of the enzyme systems.

1.2

Methods and technology of preserving food products and raw


materials

Large amounts of food products in the CIS countries are lost at the stages of raw-material
production, processing, transportation, storage and, finally, sales. A considerable amount
of potatoes, milk, grain, meat perishes as the result of losses in harvesting, transportation
and storage.
The use of polymer materials makes it possible to preserve the quality and significantly
reduce the losses of food products.
At the stages of raw-material production, polymer materials are mainly used in growing the agricultural produce, in raising and sagination of domestic animals. One of the important areas of polymer use to increase the crop yield is the presowing treatment of seeds.
It consists of spraying the seeds with a polymer suspension, which includes nutrients, trace
elements, plant-growth regulators, insecticides and other biologically active substances.
The basis of film-forming compositions are water-soluble polymers with specific

10

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

physicochemical and physicomechanical properties and the possibility of providing a


hydrophilic/hydrophobic balance in the system. Protective films reliably protect seeds from
the action of low temperatures, from premature germination under unfavourable conditions.
The properties of the coatings are programmed depending on the biological peculiarities of
plants. This is achieved by chemical modification of a polymer (e.g., polyvinyl alcohol) in
the process of film formation and polymer structure change both at the molecular and
supramolecular levels.
The climatic conditions in many cases make it necessary to grow fruits and vegetables
under coverage. The major factor, which limits the possibility of growing vegetables, berries, fruits and other crops in unprotected areas is insufficient warmth. The temperature conditions can be adjusted using hothouses, hotbeds, covers and other cultivation
constructions. Only these agricultural constructions can significantly improve the temperature conditions in the plant-vegetation zone. These constructions prove economically efficient if fabricated using polymer-film materials, which, though inferior than silicate glass
with respect to life time, are cheap, transportable and easy to erect. The major factor causing
the ageing of polymer films is solar radiation in the ultraviolet and infrared regions of the
spectrum.
Application of polymer-film materials in cultivation constructions in agriculture is
rather efficient; however, it creates the problem of utilization of used films. Upon use and
loss of consumer properties, the polymer film retains mainly a two-dimensional structure.
It pollutes the ground and is not degraded or assimilated by the environment for about 80
years. Therefore, the use of polymer films in agriculture leads to the necessity to solve the
problem of utilization of used films or their transfer into a state in which they are assimilated
by the environment, i.e., to control the polymer degradation processes. Photochemical degradation of polyolefins leads to the formation of 2 and 2, which are assimilated by
plants. Some organometal compounds, as well as complexes of variable-valence metals
with dialkyl dithiocarbamate (usually used as thermostabilizers of plastics), catalytically
degrade products of photooxidation of polymers, e.g., hydroperoxides, in storage. Besides,
complex compounds of metals are capable of absorbing the light energy. In the interaction
of organometal compounds with hydroperoxides, the so-called Norrish reactions occur. Depending on the content of sensitizers (the ScottGilid system), polymer is subjected to degradation or the system exerts a thermostabilizing action on it. The ScottGilid system is
easily introduced into polymer together with other additives and pigments.
The requirements imposed on photodegradable polymers used in agriculture and in industries are rather stringent. They should have a guaranteed service life, good mechanical
properties, be rapidly and completely degradable after the induction period, polymer degradation products formed should not be toxic, polymers should not change their properties
in storage, the polymer composition should be easily processable into items produced.
These polymers should not be expensive.
Polymer films used to fabricate cultivation constructions strongly warm up (to a temperature of 6085C) in places of the contact with the supporting structures of the frames.
Film covers on hothouses are subjected to the action of negative temperatures, which in the
North regions reach 19 to 40C. Calculations show that in the North-West and Central
European regions of the Russian Federation, in the Urals, in Western and Eastern Siberia,
in the Ukraine, Belarus, Uzbekistan, Latvia, Estonia, Moldova, Turkmenistan the thickness
of films from light-stabilized polyethylene for covering hothouses should be no less than
0.15 mm. Research showed that harvest quality and crop yield are practically the same at
different UV transmission degrees. Therefore, films with UV radiation-absorbing

CHAPTER 1

11

stabilizing additives can be used when growing most agricultural crops in hothouses. The
most widespread type of film used in hothouses in Western and Eastern Europe and the
USA are polyethylene films. This is due to their comparatively low cost, simple production
technology, possibility of manufacturing wide formats and other advantages, e.g., the simplicity of introducing various modifying additives. For these purposes, polyethylene of specials brands was manufactured.
Of film materials used for growing agricultural produce under coverage, mention
should be made of heat-resistant polymer films for disinfection of hothouse grounds with
live steam. This is the basic method of disinfecting hothouse grounds. It was invented in
Holland, but a Russian development is also available. According to this method, to increase
the efficiency of steaming (which kills all kinds of pests of agricultural crops) the ground
to be steamed is covered with a polymer film, which contributes to faster and deeper steaming. The ground is covered with the film, which is fixed with sand bags along the perimeter.
Live steam at a temperature of 115120C is fed under the film. The ground and the film
is acted upon with steam of a slightly lower temperature (90100C). One cycle of steaming
provides for holding the film at a high temperature (90100C) for 12 h, and then for
another 12 h to cooling.
Apart from growing fruits and vegetables in hothouses, films are also used to arrange
small-size covers cultivation constructions whose size does not allow the handling of
plants and harvesting inside these constructions. Such constructions include skeleton covers
for growing plants, tunnel film covers; to some extent, special perforated films are also applicable. In the latter case, the supply of heat to the ground in the spring and the warming-up
of the soil are much greater than in an open plot. A wide-format film 2030 m thick is
also efficiently used for covering sown crops and plantings without wireframes (the edges
of the film are buried into the ground 510 cm deep). The thin film does not prevent the
plant growth and provides for the hothouse effect required. Only perforated films are used
for this purpose. Though skeleton-free coverings are less efficient as compared with skeleton ones, their total economic efficiency is higher.
Removal of the films should be done by hand and is associated with pollution of the
environment, in connection with which a number of problems arises. One of the efficient
ways of solving them is to use films with a given lifetime, upon expiry of which the films
are degraded under the action of light, moisture and other natural factors to produce forms
assimilable by the environment. Degradation of the film on skeleton-free covers can start
in 20 to 70 days, but this time strongly depends on weather conditions.
Besides the described methods, polymer films are successfully used to make winter
coverings of fruits and berries, hay etc.
Mulching is an agrotechnical technique to prevent evaporation of moisture and formation of a soil crust, to maintain an optimal temperature of the soil and to suppress the growth
of weeds. Film mulching is used both in unprotected grounds, and inside film-covered hothouses and tunnels. Polyethylene films are the most widespread; they can be transparent,
semi-transparent, non-transparent, light- and heat-reflecting (white and aluminiummetallized). The greatest warming-up of the soil is observed in mulching by lighttransparent films, the use of which ensures a 4050% greater heat supply to the soil than in
an open plot. Semi-transparent films decrease the soil warming-up from 50 to 8090% depending on their integral light transparency. Reflecting films smooth the total amplitude of
soil temperature variations owing to the warming-up during the day and the delayed cooling
during the night. Coating the soil with cuts from metallized polyethylene films reduces the
extent of damage (owing to the illumination of the low side of the leaves) of undersized

12

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

vegetable plants by some species of insects (aphids, flea beetles and bugs). Black mulching
films detain evaporation of moisture, but prevent penetration of solar radiation to the soil
surface. Film mulching enhances the biological activity of the soil; herewith, the amount of
microorganisms in the soil and their activity change, the illuviation of readily soluble nitrogen fertilizers from the soil is delayed.
Mulching of the soil in cultivation constructions can be done most rationally by used
films for covering hothouses, as well as secondary polyethylene films.
Mulching by light-reflecting films in winter hothouses, when there is not enough light,
has become widespread. It improves the illumination conditions and increases the early harvest by 1525%. Additional illumination at the expense of the light reflected by the film
accelerates the ripening of strawberries, salads, kohlrabi in winter hothouses. A black film
for mulching, PE-157 brand SM (GOST 10354-82), was developed and is manufactured in
the CIS countries. Light-transparent photodegradable films PE-108-70 and PE-108-71 are
used for short-time mulching of vegetables and berries, potatoes and other crops. Besides
them, CIS industries also manufacture film materials of other types used for mulching in
unprotected and protected ground. In agriculture, fibre- and tissue-reinforced films are used
for growing and storing vegetables and fruits. By their optical characteristics, they are
slightly worse than polyethylene non-reinforced films. Reinforced films can be used at a
temperature from 60 up to +60C. They are mainly used for erecting cultivation constructions of protected ground (greenhouses, hothouses, coverings). The service life of the constructions is in this case longer (as compared with non-reinforced coatings), especially in
regions with increased wind and snow loads. Buildings and constructions from reinforced
polymer film materials are conditionally divided into three types: awnings, pneumatic constructions, skeleton constructions.
Skeleton constructions are distinguished by large reliability and do not require the use
of high-strength air-impenetrable materials. They are best of all to be used for growing and
storing horticultural produce. Skeleton-film warehouses and storages of horticultural and
other agricultural produce can be built quickly (35 days) and require no large capital investments or additional lighting. If it is necessary to make the premises darker, two-layer
coatings are used, the lower layer of which is light-impenetrable and which are fabricated
from, e.g., polyethylene filled with carbon black.
Foodstuffs can be protected from harmful substances getting into them by correctly
using the protective properties of polymer materials. It is important not only to grow a heavy
crop, to harvest it, but, which is especially important, to preserve it (not only from the point
of view of quantity, but also quality) up to the very moment of food consumption.
The problem of food preservation interested the man since long time ago. It was solved
differently at different times by different peoples.
The problem of food preservation emerged in connection with the need to store up food
reserves for oneself, ones own tribe, equpping an expedition, equipping an army etc.
Subsequently, formation and development of microbiology made it possible to lay the
scientific foundation under various technological techniques of food preservation. It proved
that the vital activities of microorganisms, which contribute to the spoilage of food, manifest themselves under conditions of a certain temperature regime, certain humidity, absence
of substances aggressively interacting with substances from which microorganisms consist,
etc. If the conditions do not correspond to those required for the development of microorganisms, the latter perish or their vital activities are temporarily stopped and, therefore, the
process of food spoilage stops, too.
A widespread technological technique of preserving food products is drying. The

CHAPTER 1

13

technique is based on the fact that most chemical processes determining the vital activities
of bacteria occur in an aqueous medium. Removal of water leads to the inhibition or interruption of chemical reactions contributing to the development of microorganisms and accompanying food spoilage.
In cells of fresh products, the food substances are, as a rule, in solution. In the course
of drying, the concentration of this solution increases until it becomes so high that the solution can not be absorbed by the cells of various microorganisms any more. At the extent
of drying, corresponding to the above situation, a food product can be stored without deterioration of its quality for a long time. The content of moisture in it should be observed not
to be higher than a certain limit: 1214% for dried vegetables, 1825% for dried fruits. The
smaller is the moisture content in the product after drying, the greater the guarantee of its
preservation is, the less the conditions for spoilage are.
However, the lower the moisture content in a dried product is, the more complicated
and, therefore, expensive the process of drying is. Besides, some substances useful for the
organism can be destroyed in the process. During the drying, water is evaporated from particles of the product and vapours formed are carried away. Drying is performed most often
using hot air, which, being a heat carrier, communicates a heat energy to water molecules.
Owing to the acquired energy, water molecules overcome weak physical and physicochemical bonds and pass from the product into the vapour. The higher the temperature of the air
is, the more water molecules pass into the vapour, i.e., into the heated air.
The moisture capacity of the air is different at different temperatures. This method is
used to increase the storage life of fruits, vegetables, milk, meat, fish and other foodstuffs.
In drying apples and pears, mainly early varieties are used. Primarily fruit drops are
dried. It is best to dry fruits of one variety. In the summer, fruits usually dry up in 34 days.
Before drying, fruits are washed. Washed fruits are examined to cut the damaged parts, the
cores are excised and the fruits are cut into slices not more than 1 cm thick. Small fruits and
pears can be cut into two or four parts.
A method of preserving products by drying at low temperature freeze-drying is of
an ever increasing importance at present.
The process of sublimation (removal of moisture at low temperature, when a product
is preliminarily frozen) can be greatly accelerated by removing water vapour by direct
pumping out (evacuation), condensation of vapours on a chilled surface, absorption of vapours by hygroscopic substances. The use of the method of freezing for preserving food
products revealed the phenomenon of structure breakdown of plant and animal tissues by
growing crystals of ice. To avoid this undesirable phenomenon accompanied by the loss of
a number of useful specific properties of food products, the following technique is used.
Products are chilled so rapidly that ice crystals have no time not even to grow but to be
formed. Products prepared for freeze-drying are frozen and placed into a chamber, from
which the air and vapours are pumped out. If pressure in the chamber decreases from the
initial magnitude (of the order of 760 mm Hg) down to 11.5 mm Hg, water could not be
in a liquid state under these conditions and passes from the solid state (ice) into the gaseous
state by omitting the liquid state, i.e., it evaporates. Transition of a substance from the solid
state into the gaseous state by omitting the liquid state is called sublimation. The vapours
formed are pumped out by vacuum pumps, and water is gradually removed from the frozen
product. It dries at a low temperature.
One of the main requirements to drying, as to the other preservation methods, is the
maximum preservation of the nutritive value of food products. Numerous studies of the biological and nutritive value of food products subjected to various methods of drying have

14

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

been carried out with this in mind. The results of studies convincingly showed that the best
integrity of food products and their nutritive value is provided for by the method of freeze
drying. This refers equally to products of both plant and animal origin.
Removal of water from a food product drying is a forced measure, which is due to
the necessity to inhibit the chemical reactions occurring in storage. After the storage, the
product should restore its initial properties and the initial content of moisture. Therefore,
the reversibility of the drying process is essentially determined by the capability of the dried
product to swell again in contact with water. A relative increment (with respect to the mass
of the dry product) of mass in swelling is called the extent of swelling. The extent of swelling of freeze-dried mutton was 3.5%, whereas that of heat-dried mutton only 2%. In other
words, meat after freeze-drying increased its mass 4.5-fold in 4045 min, after which no
increment was observed: all water, which the freeze-dried meat was capable of absorbing,
was absorbed. The process of water absorption is also observed in heat-dried meat. However, this process was slower than in freeze-dried meat, and it was completed only after
2.53 hours of swelling. The mass of heat-dried meat, after it absorbed the maximally possible amount of water, increased only three times. This difference in the swelling of
freeze-dried and heat-dried mutton is explainable by the denaturation of proteins and thickening of muscle tissue. Freeze-dried meat, being boiled after 12 months of storage, preserved its culinary and organoleptic properties. The caloric value of freeze-dried mutton is
3.5 times as large as that of raw meat. Heat-dried meat is close to freeze-dried meat by its
caloric value. However, by its organoleptic properties (taste, smell, appearance)
freeze-dried mutton is much better than that of heat drying. Fat on freeze-dried mutton
chops does not differ from raw meat. A heat-dried duck broth is usually turbid and has an
unpleasant taste. A broth from freeze-dried meat tastes good and has the specific flavour of
a duck broth.
A similar pattern is observed in comparison of freeze-dried and heat-dried fish. Thus,
proteins of freeze-dried meat of pike perch preserve their properties better than proteins of
heat-dried meat. Only insignificant changes in the composition of its proteins were observed during the storage of freeze-dried pike-perch meat. The specific composition of liver
oil determines its oxidation susceptibility. After a 12-month storage of freeze-dried meat of
pike perch, vitamin B1 was totally preserved. The extent of swelling of freeze-dried
pike-perch meat reached an equilibrium value in 3040 min and was 3.5. The swelling
equilibrium of heat-dried meat was established only in 3 h and was characterized by the
swelling extent of 2.2. It is known that the culinary properties of heat-dried meat of pike
perch leave much to be desired. But the broth from freeze-dried pike-perch meat, obtained
by boiling for 1517 min, has a good taste and flavour. Similar results were also obtained
in comparative studies of heat-dried and freeze-dried fillet of common carp. The caloric value of freeze-dried common carp meat proved almost five times as high as that of raw meat.
Freeze drying involves freezing of a product. However, it should be noted that freezing
of food products is of independent significance, not necessarily associated with drying of a
product. Chilling of foodstuffs can be used both for drying and with the aim to inhibit the
spoilage process without freezing the product itself. This goal is pursued in storing products
in refrigerators. But cold can also be used for freezing products with the aim of their further
processing. In the former case, products should be kept intact during the chilling, having in
mind not only mechanical damage but also the integrity of cell viability. Herewith, the biochemical processes continue in the products stored but, naturally, at a slower pace. The metabolic processes in, e.g., chilled fruits and berries are active, they breathe and ripen.
Freezing of foodstuffs is accompanied by significant changes in their tissues and cells. The

CHAPTER 1

15

moisture in them freezes and turns into crystals of ice, which grow and partially destroy
cells. Moisture freeze-out is, in turn, accompanied by dehydration of the liquid part, in
which the nutrient materials of the cells are dissolved. During the unfreezing of such products, the moisture formed in thawing of ice crystals can not be absorbed by the cells, which
underwent irreversible changes. Unfrozen products abundantly ooze juice. However, undesirable phenomena associated with the growth of crystals in freezing could be avoided. For
this purpose, the process of freezing should be very quick not to let ice crystals to be formed.
The matter is that for crystals, in particular, ice crystals, to be formed, their constituent molecules and atoms should be arranged in space in a strict order relative to one another. The
lower the temperature, the larger the viscosity of the liquid is. Therefore, if the cooling is
performed quickly, then, starting from some temperature, the rearrangement of the structure
has no time to be completed. The temperature is so low that a crystal should have formed,
but the structure remains the one corresponding to the liquid state. Molecules can not move
in space, but perform vibratory heat motions. There are no crystals and, thus, no irreversible
changes of the cells and tissues of frozen products take place. Therefore, to obtain a higher
quality of frozen products in modern refrigerating industry, the freezing process should be
performed quickly, with an intensive removal of heat, at as low temperature as possible. In
rapidly frozen products, the cell envelopes mainly remain unbroken. Therefore, there is no
juice oozing out after such products are unfrozen. Modern freezing installations usually provide for the coolant temperature within 25 to 35C. A product is frozen to 18 and is
stored at this temperature. During the storage, periodic temperature increases should be
avoided, as an increase of even several degrees is accompanied by the recrystallization of
ice, growth of separate crystals with all ensuing consequences.
To manufacture high-quality fast-frozen products, it is necessary to provide for the
freezing of manufactured semi-finished products in a fast freezer, storage of frozen products
in a refrigerator chamber of the plant, transportation of the products in refrigerator railroad
cars or refrigerated road vehicles for their sales. In shops, these products should also be
stored in distribution refrigerators or chambers. After purchasing rapidly frozen produces,
consumers should keep them in refrigerators, without allowing even for a short-time thawing. Manufacturing of high-quality frozen products is associated with expenditures for complex refrigerating equipment. However, when comparing various methods of foodstuff
preservation (sterilization, drying, pickling, marinading, addition of preservative agents), it
should be stated that in fast frozen foodstuffs the quality of the product preservation of
taste, culinary merits, vitamins, aromatic substances proves the highest.
At present, the domestic industries manufacture a broad range of fast-frozen foodstuffs. They include various kinds of fruits and vegetables, as well as products of a high
degree of doneness, such as vegetable, meat-and-vegetable and fish first and second
courses, fruit juices.
The process of freezing proceeds the most qualitatively and efficiently in special fastfreezing machines. Storage and transportation of frozen products requires their packaging
in hermetic and moisture-proof containers. If these conditions are not observed, during the
storage of frozen products in chambers at a temperature of 15 down to 18 the moisture
will be sublimed into the air bathing the products. The moisture that passed from the product
to the air is condensed at cold pipelines, walls, ceilings as frost. The layer of accumulating
frost prevents the transfer of heat from the freezing product to the coolant. Thus, nonhermetic or moisture-permeable packagings will cause the loss of weight of a freezing product, deterioration of its quality and worsening of heat-exchange parameters. Usually, loose
frozen products are poured onto tables covered with tin-plate sheets and packaged into

16

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

containers. Above, we mentioned the necessity to maintain the temperature of a frozen


product constant both in storage and in transportation, as otherwise ice-crystal growth will
take place with the ensuing consequences.
Fish meat is in most cases less prone to deterioration when frozen by traditional methods. However, during the storage in refrigerators evaporation of moisture takes place, which
is accompanied by the penetration of ice crystals into the tissues. To prevent losses and
quality deterioration of fish products, a new cryotechnology for processing polymers from
aqueous solutions was developed. A protective coating is formed on fish products without
any additional energy expenses. Two types of food coatings, Polyol-1 and Polyol-2, were
developed. The second coating contains preservative agents for the inhibitory action on microflora and a structure former to produce an elastic transparent coating with a long lifetime.
Fresh fish is to be coated, which makes it possible to preserve additionally large quantities
of a valuable product lost at the stage of preliminary freezing. The process for the Polyol-1
protective coating was implemented at the Gurievrybprom Production Enterprise of the
Kaspryba All-Russian Industrial Association for long-term refrigeration storage of frozen
fish.
An incorrect choice of material for containers and packagings of frozen products,
the same way as an incorrect packaging of a product, can render null all professional actions
of sorting, calibration, washing, cleaning, cutting, chopping, freezing and other process
operations.
Considering the methods of preserving food products, we can not but dwell on one of
the classical methods preservation by heat. Vegetables for preserves, the composition of
which includes, besides vegetables, only water and some salt and sugar for good taste, are
subjected to washing, calibration, cleaning, cutting and blanching. The caloric value of such
preserves is not high, but they keep almost all valuable properties of preserved vegetables.
This applies to their taste, flavour and food value. Most vegetable natural preserves are sterilized by heating above 100C. For instance, green peas are preserved, when their grains
are green, soft and sugary. Usually at this stage of ripeness, their grains contain 57% sugar,
2030% vitamin C, proteins and mineral substances. Prepared grains of green peas are
blanched at 9098 for 34 min, after which the grains are immediately cooled to avoid
overcooking. Green-pea grains thus prepared are packaged into tin-plate or glass containers, and a hot filling is poured in. The filling consists of sugar (23%) and salt (23%) dissolved in hot water and should be filtered before use. Sealed containers are subjected to
sterilization by heating to kill microorganisms, which cause spoilage of the product. In industrial conditions, such a sterilization is performed in autoclaves hermetically closed cylindrical steel boilers. The higher the sterilization temperature is, the sooner the sterilization
is completed, i.e., the less time is required to kill microbes. However, too high sterilization
temperature can lead to a deterioration of the quality of the preserves: darkening of the product, an unpleasant flavour etc. These changes are usually due to undesirable chemical reactions between the components of the product at too high temperatures, which do not occur
at lower temperatures. The sterilization temperature is determined by the resistance of microbes to high temperatures, which essentially depends on the acidity of the sterilized product. Usually, bacteria not forming spores perish during the boiling. Sporulating bacteria
perish only at a long-time heating up to 110120. In an acidic medium, e.g., in tomato
or sorrel puree, bacteria do not develop. However, in such products spoilage is due to molds
and yeasts, which perish in boiling. Products with a low acidity are sterilized at temperatures of 112120. Large containers are heated up slower, low flat cans are heated up
faster than high ones.

CHAPTER 1

17

Besides temperature, size and shape of cans, the sterilization time is also determined
by the consistence of the product. The more densely the product, e.g., paste, fills a can, the
more time is required for the necessary temperature to be established in the middle of the
packaging. Besides the thermal conductivity of the contents of the packagings, the sterilization time is also determined by the thermal conductivity of (iron, glass or polymer) containers, as well as the initial temperature of cans. Therefore, its own regime of thermal
sterilization should be chosen for each kind of preserves and each type of cans, based on
the above conditions.

1.3

Technology of preserving the quality of foodstuffs in manufacturing,


transportation and sales

In production of foodstuffs, of great importance for preventing losses and spoilage, as well
as corrosion of food equipment is the use of antiadhesion coatings.
An optimal coating for baking rye bread was developed and is used at the St.-Petersburg Bread-baking Plant No 12. Besides the economy of oil, the antiadhesion coating saves
a considerable amount of flour, eliminates expenses for oiling and cleaning of molds, facilitates the application of automatic machines and, which is of no small importance, enable
increasing the quality of baked goods. In molds free of burnt deposits the required temperature is easier to maintain, losses of bread are much smaller, the work of oven operators is
much easier. Antiadhesion polymer coatings are applicable in other branches of food industry, e.g., in meat and dairy industry. Some components of the equipment in food industry,
in particular, shelves and racks for storing and ripening cheese are made from wood and
have a number of disadvantages: they are short-lived, are characterized by a highly labourintensive service due to stickage of cheese and integrated sanitation treatment, during which
wood warps. Besides, labour-intensive process operations can not be mechanized in this
case. Shelves and racks can be fabricated from cheep carbon steel coated with a polymer
coating, which should possess a low adhesiveness to foodstuffs and necessary physicomechanical and sanitation properties. The most important requirements to such coatings in
operation are the stability of antiadhesion and physicomechanical properties, protection of
the metal equipment from corrosion under conditions of high humidity within the temperature range of 10 up to 80. Material with the required properties can be produced by targeted modification of non-critical and physiologically harmless polymers, e.g., highdensity polyethylene (HDPE). To eliminate the cracking of HDPE-based coatings in their
operation in aggressive moist media, HDPE was modified by polyethyl siloxan PES-5, as
the result of which HDPE was stabilized, and the antiadhesion properties of the coating improved.
The most labour-intensive operations in fabrication of molded meat products include
dislodging of a product from the mold and the subsequent cleaning of its surface. Interlaying materials cellophane and cooking parchment paper are used inefficiently to provide for the separation of a product and a mold. Animal fat is used for greasing the molds
in production of meat loafs, as the result of which a deposit is formed on the molds. The
quality of the products and the sanitary condition of the production shop deteriorate in this
case, the molds should be subjected to systematic cleaning, which makes difficult the mechanization and automation of the processes. All these drawbacks can be eliminated by using
antiadhesion coatings.
In the process industries of the agroindustrial complex, of great significance is the protection of equipment from corrosion. In this respect, it is difficult to overestimate the role

18

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

of antiadhesion coatings which by their sanitary characteristics are permitted to be used in


contact with food products. The problem of corrosion is very significant, though achievements in this field are quite a few, the domestic developments including.
One should take into account the losses of manufactured food products in storage,
transportation and sales by commercial enterprises. Various compositions for the protective
coating of food products are known. Thus, a composition was invented, which protects
cheeses from drying and molding. A composition for coating sausages and a method of producing a casing on them were proposed. A composition for applying a protective coating
on fish and fishery products was also developed.
The most promising method of long-time preservation of the nutritive properties of
food products is their low-temperature preservation. However, a considerable amount of
weight of a product is lost in freezing and subsequent storage due to evaporation of moisture, the quality of a product deteriorates, oxidation of lipids and denaturation changes of
proteins occur. One of the rational ways to retain the quality of products is to create coatings
impermeable for oxygen and moisture on their surface. For this purpose, aqueous solutions
of biologically inert polymers, e.g., polyvinyl alcohol (PA) are used. PA acquires water resistance in the process of film formation at low temperature. During the freezing of the
polymersolvent system, as the result of a phase transition accompanied by an abnormal
increase of its volume, PA undergoes mechanochemical transformations (cryolysis). Cryocracking of macromolecules is accompanied by the emergence of active cryolyzates, whose
interaction leads to the formation of insoluble spatial structures.
The topicality of the problem of using advanced polymer materials determined the necessity of international forums exhibitions and symposia dedicated to this problem. The
cost of a packaging was on average 8% of the cost of product. There is a tendency in European countries to sell foodstuffs in packagings convenient for preparation of food in microwave ovens.
Great attention is paid to the process evaluation of the packaging systems from the environment-protection point of view. Among the main tendencies of the packaging business
in the USA, it is necessary to note the development and commercial production of ecologically pure packagings, a decrease of pollution of the environment. There is a tendency to
move from multi-layer to single-layer packagings, e.g., single-layer bottles from polyethylene terephthalate (PET), which are easy to identify and reprocess. Packagings are used,
in which deep-freeze dishes can be warmed in microwave ovens (PET). Thus, Gortons
place fish sticks into a packaging, which is equipped with elements from metallized PET
film above and below. The elements are susceptible to the absorption of microwaves, which
leads to the effect of a crunchy crust. Special attention is paid to the use of renewable resources (wood, plants). In this respect, of interest is the packaging material based on ethrol,
which under certain processing conditions can be transferred to a liquid-crystalline state.
Packaging in a film material in liquid-crystalline state is rather promising.
Polymer packaging materials found wide use throughout the world, Russia including.
Expanded production of polymer film materials is restricted only by deficit of the initial
materials. For this reason, it is possible to organize production of polyisoprene hydrochloride-based polymer films with good sanitation parameters, in contact with fats including, which easily yield to two-dimensional strain and shrink after orientation at 70C. The
initial materials are polyisoprene (whose output reaches several million tons per year), HCl
and methyl chloride (which should be subjected to recuperation), a small amount of sorbic
acid (used as food stabilizer at present). The method of producing a film-forming material
based on polyisoprene hydrochloride was developed well back in 1960s.

CHAPTER 1

19

Multilayer films became widespread in the world practice as packaging materials. The
first domestic multilayer film for packaging non-fat food products was a film from polyethylene and cellophane, which was improved and found widely used for packaging food
products (not of increased fat content). Cellophane is produced from naturally renewable
raw materials, is biologically harmless (at a corresponding control of production), possesses
the barrier properties, which significantly deteriorate when it is moistened. A disadvantage
of cellophane is its incapability of heat sealing, which greatly worsens the packaging process of food products. A combination of these materials produces a film heat-sealed material with high barrier properties. However, as the inner layer is polyethylene, this material
can not be in contact with fatty food products. Progress in the development of multilayer
film materials in this and other countries was accompanied by the emergence of multilayer
films with different combinations of paper, foil, various polymer films and binders. The
problems one comes across in this case are pollution of the environment and interaction of
a foodstuff with the packaging. Regularities of the interaction of a foodstuff with the packing and with the environment are being revealed. The most important processes of this king
are penetration of oxygen, water vapours, light and carcinogens from the atmosphere into
a foodstuff through polymer films. Substances contained in the foodstuff can get to the environment through the packaging. These processes are undesirable.
In the recent years, the use of the vacuum freeze drying of food products has become
more widespread, and the popularity of this method has increased. Production of foodstuffs
by this method has both positive and negative aspects.
The positive aspects include the high quality of these products; by their nutritive and
gustatory properties, they are comparable only with natural deep-frozen products (studies
by E.I. Kaukhcheshvili). A positive quality is also the capability of long-time storage (up
to 1 year and more) under non-regulated conditions of the environment. A drawback is the
high cost of vacuum freeze preservation; as shown by B.P. Kamovnikov, average reduced
costs for the removal of moisture from an object of vacuum freeze drying exceed similar
expenses for heat drying 1520 times.
A quite natural and justified idea would be to reduce the costs of preserving freezedried products several times without decreasing the high consumer properties. Calculations
show that, though this is difficult, this problem is quite realizable technically: to solve it,
the freeze-drying process should be performed not in a vacuum, but at an atmospheric pressure. This would, first, make it possible to exclude the expensive and energy-intensive vacuum equipment from the process. Second, at an atmospheric pressure heat-and-mass
transfer could be intensified (especially at the final stage of drying) due to the convection
of the drying agent, which is out of the question under vacuum conditions. In other words,
for production of daily-consumed freeze-dried products the vacuum freeze-drying should
be replaced with atmospheric freeze-drying (AFD).
In a general case, the process of preservation by the AFD method includes the following major operations: sorting and treatment of raw materials, freezing, removal of moisture
by freeze drying at negative temperatures, cold and hot completion of drying to a given final
moisture content, prepackaging and packaging of the dried product. The properties of the
preserved products crucially depend on the condition of raw materials and the quality of
performing each of the above operations. Herewith, the preservation process has its peculiar
features for each particular kind of product, depending on the properties of raw materials
and requirements to the final product.
It should be pointed out that materials dried by the AFD method are rather hygroscopic
and have a large specific surface of the dry carcass.

20

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Objects of drying

Raw materials for production of


medical preparations / biostimulants

Foodstuffs
Foodstuffs of animal origin

Endocrine / enzyme raw


materials of animal origin
Crude drugs of plant origin
Figure 1

Foodstuffs of plant origin


Sea foods

Classification of objects of drying.

For this reason, long-term storage without reduction of quality can be possible only in
a reliable hermetically sealed packaging. With any other conditions equal, the duration and
quality of storage are basically determined by the quality of packaging. For instance, the
use of metal tin-plate cans or multilayer metallized films for fabrication of packages and
the filling-up of these containers with a dry product with gaseous nitrogen makes it possible
to provide for the storage of plant products in the off-season period.
As the preservation by the AFD method is a sufficiently complex process, and the preserved products are usually intended for long-time storage, the requirements to the initial
raw materials are high. The nutritive value and vendibility, structural mechanical properties
and admissible terms of storage, the temperature level of processing and duration of individual process operations all these are largely determined by the properties of the raw materials. Along with the diversity of the chemical composition of various food products, they
are characterized by one common property: they contain a considerable amount of water.
As objects of processing (including by preservation by the AFD method), products are
classified by their physical nature into objects of animal and plant origin and sea foods. By
their consumer properties, a separate group is endocrine / enzyme raw materials, which are
usually not used as a source of food, but are an essential source in production of medicines
and biologically active substance.
A classification of objects of drying is presented in Fig. 1. The purpose of products is
taken as the first-rank classification criterion. Two large groups are singled out here foodstuffs and raw materials for production of medical preparations and biostimulants.
The second rank of classification is chosen to be the characteristic of dividing the
objects by their physical nature. Individual groups of objects of drying singled out at the
second-rank level differ significantly by their composition, physicochemical and other
properties (Table 1.1). For this reason, the possibility of using methods of vacuum or atmospheric freeze drying for their preservation and the choice of drying regimes should be decided upon separately for each group of products close by their properties.
A complex interaction of these components with water and with one another forms the
properties of food products. The amount of water in a product also determines the conditions of its storage, which would not reduce its quality.
Meat used for preservation by the AFD method should conform to a number of requirements. Cartilages, large vessels and connective tissue are removed during the trimming in
the preparation of meat for drying. These inclusions considerably differ by their heat transfer properties from muscle tissue, their presence would lead to nonuniform drying, worse

21

CHAPTER 1

rehydration of the dry product, would reduce vendibility and gustatory qualities of culinary
products made using the dry product. A high content of fatty tissue is inadmissible. The
melting temperatures of animal fats are rather low (e.g., beef fat, 3252C; pork fat,
2848C; chicken fat, 2338C). For this reason, at the stage of residual moisture removal
(completion of drying) fat can melt and fill free pores, which would sharply increase the
duration of drying and formation of non-drying inclusions (lenses) in the depth of the specimen. Besides, at the stage of storage of dried meat the oxidative transformations of the lipid
fractions can drastically deteriorate the organoleptic parameters of the product. These
changes can be the largest in pork and poultry meat, as fats of these kinds of meat contain
many unsaturated fatty acids.
Table 1.1
Product

Pasteurized milk
No fat curd cheese
Common beef
1st category hens
Hens eggs
Azov-sea carp
Potato
Cabbage
Mushrooms
Apples
Black currant
Apricots
Plums
Bulb onion

Water,
%

Proteins,
%

Fats,
%

Carbohydrates,
%

Fibre,
%

Ash,
%

88.5
77.7
71.7
61.9
74.0
75.3
75.0
88.5
88
85.6
85
86
87
86

2.8
18.0
20.2
18.2
12.7
18.4
2.0
1.3
1.8
0.4
1.0
0.9
0.8
1.7

3.2
0.6
7.0
18.4
11.7
5.5
0.1
0.1
0.8

4.7
1.5

0.7
0.7

19.7
7.0
1.1
11.3
8.0
10.5
9.9
9.5

1.0
1.2
1.5
0.6
3.0
0.8
0.5
0.7

0.7
1.2
1.1
0.8
1.0
1.0
1.11
1.0
0.4
0.5
0.9
0.7
1.3
1.0

Energy value,
100 g/kJ
243
360
602
1008
657
506
374
138
79
192
167
192
180
180

The requirements to the raw materials intended for preservation by AFD are satisfied
the most by meat of young animals. The muscle fibres of this meat are more thin and elastic,
meat possesses a relatively lower mechanical strength, the content of fat in it is small.
An important factor in producing a high-quality product is the dependence of the properties of meat not only on the tissue and chemical compositions, but also on the depth of
autolysis. According to the obtained recommendations, meat after a 3- or 4-day holding at
24C should be used for preservation by freeze drying.
When choosing the AFD regimes for milk and dairy products, it should be taken into
account that the properties of milk proteins change in heating and freezing. Thus, in freezing
(down to temperatures below 10C), the colloidal properties of milk proteins change, their
solubility decreases. Milk fat in the milk mass is distributed in the form of balls up to 5 m
in diameter, each of which is enclosed by an envelope containing a protein complex. In the
contact of lipid fractions with oxygen of the air during the AFD process or in storage of a
dry product, the product can rancidify and suffer a deterioration of taste. For this reason,
when packaging dry milk and dairy products it is necessary, as in the case of packaging dry
meat products, to use hermetic vapour- and light-impenetrable containers filled with inert
gas. Products prepared from no fat milk are more resistant.

22

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Milk sugar (lactose) is close by its nutritive value to common beetroot sugar. However,
a larger content of reducing sugars in milk and dairy products (e.g., in mare milk, up to 7%)
creates conditions for sugar-amine reactions in storage of dried products. For their maximum inhibition, it is necessary to remove moisture from dairy products in the process of
drying up to 23%. In practice, during the preservation by the AFD method this condition
is achieved by drying dairy products in air convector heaters (furnaces) at temperatures of
4050C upon completion of the moisture removal by the icevapour phase transition.
Freeze drying of milk, curd, many fermented milk products makes it possible to preserve maximally the high quality of the product produced. And for such products as, e.g.,
acidophilic paste and Mechnikovs sour milk, it has no alternative.
The recent decade is characterized by an increased production of new kinds of products based on combinations of meat raw materials with proteins of plant and animal origin.
Among protein preparations used for partial replacement of meat raw materials, compositions used the most are milk proteins (sodium caseinate, milkprotein concentrate etc.) as
well as soy proteins (soy isolate, soy concentrate, soy flour and grits). Numerous experiments have proved that a rational level of the substitution of protein for meat raw materials
is from 10 up to 30%, depending on the kind of protein used.
Introduction of rehydrated protein preparations into the meat system raises the stability
of the dried meats lipid fraction to oxidation and increases the storage times, raises the resistance to thermal denaturation, provides for the balance of the amino acid composition,
improves the organoleptic properties of culinary products prepared from reconstituted dry
products. An especially important fact is the possibility of drying and freeze drying of meat
products with protein additives at a higher temperature as compared with meat products
containing no protein fillers. A temperature increase could be 56C without the loss of
quality, which enables saving energy and in some cases using a simpler equipment.
Milk and soy proteins are widely used at present for enrichment of meat products. Milk
proteins are added into chopped meat as sodium caseinate. The substitution of sodium ions
for calcium available in milk has a positive effect on the increase of solubility of the protein
and imparting it with the properties of a water-binding and fat-emulsifying component.
Precipitation of casein with whey proteins yields preparations containing all milk proteins, the so called coprecipitates with up to 80% protein in the dry residue.
Processing of soybeans to obtain food proteins is performed in several directions,
which enables production of soy flour and grits containing about 50% protein: soy concentrate (produced from soy grit, from which soluble carbohydrates are removed and protein
passes into an insoluble form), the content of protein up to 70%; soy isolate (highly purified
protein preparations without taste and smell), the content of protein up to 90%. Integrated
studies of the chemical composition of some kinds of protein preparations show that all protein preparations are characterized by a high protein content and a low fat content.
Soy protein preparations contain essential vitamins and mineral salts.
A comparative analysis of the amino acid composition indicates that plant protein
preparations are characterized by a lower content of sulfur-containing amino acids as compared with proteins of animal origin. However, when soy proteins are used in a complex
with proteins of animal origin (muscle protein, caseinate, blood plasma) their biological activity increases due to the mutual enrichment with essential amino acids.
In the freeze drying of eggs, a mixture of egg white and yolk (a melange) or only white
is used. A promising procedure is the use of eggs for preparing products with a whipped
structure meat, milk or fruit souffle, which are then preserved by the AFD method.
The presence of various enzyme systems in eggs leads to the development of autolytic

CHAPTER 1

23

changes in their storage, the general tendency of which is similar to the autolysis process
in animal tissues, so dietary or fresh eggs are used as the initial product. According to the
operating standard, the former are the eggs that come to the consumer no later than 7 days
from the day of laying and not kept in solutions. Fresh eggs are those that were kept at a
temperature of +2 to 2C for no more than 30 days.
Along with animal and poultry meat, fish is an essential source of complete proteins;
proteins of fish meat are easily assimilated by the human organism. Constituents of fish
meat are basically represented by proteins, lipids and water. The chemical composition of
tissues is rather inconstant and depends on the fish species, age, time of capture etc. Thus,
the relative moisture content is on average from 53 (eel) up to 81% (cod, pike perch); protein substances, 10 up to 24%. Variations are even larger in the fat content from 0.20.4
up to 30%. Fatty meat contains less water than lean meat. However, the total content of
water and fat in the fish body remains practically always a constant value close to 80%.
For atmospheric freeze drying, only the meat of fish with a minimum amount of fat
could be used, as it could be oxidized both during the drying and in storage. We should note
that, owing to a high degree of unsaturation, fish fats are easily oxidized; herewith, some
of these products can be toxic. As the result of postmortem processes, fish meat undergoes
significant physicochemical changes. The initial stage of rigor mortis is characterized by
intensive glycolysis of glycogen, accumulation of lactic acid in muscles and a pH decrease.
The further development of the processes finally leads to contraction and tension of muscles. With the course of time, rigor occurs owing to the further irreversible protein changes,
determined as maturation and autolysis. Meat becomes more tender.
Sea is also a source of other valuable foodstuffs (e.g., prawns, crabs) and raw materials
for medical industry (various algae). Freshwater reservoirs are habitats of such a valuable
source of protein and biologically active substances as chlorella. These objects can be successfully preserved by the AFD method. The qualitative indices of dry semi-finished products conformed to the imposed requirements.
A characteristic feature of all plant products is a large water content, 6696%. The
main carbohydrates of fruits and vegetables are sugars, starch, cellulose and pectin substances. Studies of plant-origin products show that the chemical composition of even one
species changes depending on the extent of ripeness, variety, growth conditions etc.
Fruits and vegetables contain all known vitamins, except vitamins B12 and D (calcipherol). Vitamins C, A (as provitamin A, carotene), vitamin K occur in largest amounts.
Plant products are the main source of vitamin C. The change of its content in the food ration
due to freezing, freeze drying and subsequent storage of the dry product is (together with
the organoleptic indices) an essential criterion of quality of the entire preservation process.
Vitamin C is easily destroyed by heating and under the action of oxygen of the air.
Thus, in the presence of oxygen of the air it breaks down already at a temperature of 50C.
This should be taken into account when choosing the temperature regime at the stage of
completion of the drying, as well as when choosing the design of the device for AFD.
Fruits and berries contain a considerable amount of sugars, from 79% (black currant,
garden strawberries, apples) up to 2025% (dog-rose, grapes). In vegetables, the content
of sugars is usually at a level of 46%. Sugars are represented by glucose, sucrose and fructose, the quantitative ratios between which are different for each kind of product. Changes
in the properties of sugars in the course of the process have a strong effect on the quality of
the ready-made product. The action of high temperatures is inadmissible, they can contribute to the caramelization of sugars, induce reactions of melanoidin formation as a consequence of the interaction of sugars with amino acids. As the result, browning of the product

24

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

takes place. Note that plant products with a significant sugar content, e.g., bananas, are practically unsuitable for preservation by the AFD method.
Fruits and vegetables contain 0.23% of cellulose, which is mainly used for construction of envelopes and cell walls. The composition and content of the cell walls determine
the mechanical properties of tissue. Cellulose is characterized by a high chemical resistance. Preservation of fruits and vegetables by the AFD method usually envisages the destruction of cellulose the preparation of purees and pastes, comminution.
The pectin substances of plant-origin products include complex polysaccharides. In
fruits and vegetables, they are 0.12% of the total mass of a product. Significant amounts
of pectin are in apples, quince, plums, apricots. Pectins have the property of forming stable
colloidal solutions. The condition of the pectin substances in a dry product largely determines the degree of its rehydration.
As shown by the experience of preserving a broad assortment of fruits, vegetables and
berries by the method of vacuum freeze drying, the ultimate choice of this or that variety
with the aim to obtain a high-quality dry product can be made only based on the experimental check in each particular case. It was found that particular varieties of plant-origin products, good by their initial quality parameters, were unsuitable for preservation (due to the
loss of shape in drying, instability in storage, bad rehydration). In full measure, this is also
valid in the case of the AFD method.
The AFD method has a great potential for preserving flavouring/spicy plants added to
foods for flavour and to excite appetite. Many savoury herbs in the form of spices have a
strong bactericidal action. In the European part of Russia, these are widely used dill, parsley,
parsnip, coriander (cilantro), peppermint and estragon (tarragon). Leaves of these plants
contain various aromatic oils, vitamin C, provitamin A, biologically active substances.

1.4

Application of chemical preservatives in food industry

1.4.1 General information on chemical food preservatives


Chemical preservatives are synthetic chemical substances used for slowing down or preventing undesirable changes in foodstuffs and technical products of biological origin
caused by microorganisms bacteria, molds, yeasts.
Chemical food preservatives include sulfurous anhydride and some salts of sulfurous
acid; benzoic, sorbic, propionic acids and some of their salts; methyl, ethyl and propyl esters
of para-oxybenzoic acid. Hexamethylene tetramine; formic, boric and salicilic acids;
formaldehyde, hydrogen peroxide have not been used lately in most countries.
Preservatives make it possible to increase the storage times of ready-made products
and raw materials, as well as prevent spoilage of raw materials in processing. Preservatives
are usually used when other methods are not possible.
Application of chemical preservations is restricted as, being toxic for microorganisms,
they are harmful for man and animals. Therefore, they are used at very small concentrations,
harmless for higher organisms and man.
In food industry, chemical preservatives are used mainly in combination with heating,
freezing, drying, irradiation etc. Their actions add up.
The method of treating a product with preservatives depends on the kind of product
and its condition. Liquid and comminuted products are usually thoroughly mixed with the
preservative. Lump products are subjected to surface treatment, e.g., by immersing a product into a solution or by sprinkling it with a solution.

25

CHAPTER 1

Treatment of the surface of a product is especially expedient when there are no microorganisms inside it.
Preservatives cause damage to microbial cells, reversible (bacteriostatic or fungistatic
action) or irreversible, as a consequence of which cells die (bacteriocidal or fungicidal
action).
At a bacteriostatic action, microorganisms remain alive, but are not capable of propagation. If they are transferred to a favourable medium, propagation becomes possible again.
However, microorganisms gradually die even at a bacteriostasis, depending on the concentration and duration of action of a preservative. In practice, bacteriocidally acting substances differ from bacteriostatic ones only by a greater pace of microbial die-off.
The rate of bactericidal action increases with the increase of the concentration of a
chemical substance and temperature.
Bacterial cells can develop, propagate, produce toxins only under certain conditions.
Bacteria, e.g., are sensitive to pH of the environment. A significant change of pH leads to
a change of the surface amphoteric structures of the cell and, owing to this, to a disturbance
of cell equilibrium followed by cell death. In particular, the osmotic exchange between the
cell and the environment is disturbed. In some microorganisms, a pH decrease causes an
activation of the ribonuclease autolytic system, which is unfavourable for cell viability.
Bacteria, with few exceptions, can develop in media with pH 4.29.4; yeasts develop
in a more narrow pH interval (4.06.8); and mold fungi, within even broader pH limits
(1.211.1).
Many preservatives of acidic type are more efficient at low pH, as a major part of them
are in a non-dissociated form (Table 1.2).
Table 1.2
Preservative acid

Sulfurous
Bromoacetic
Salicilic
Formic
p-Chlorobenzoic
Benzoic
p-Oxybenzoic
Acetic
Sorbic
Propionic
Dehydroacetic
Bisulfite
Boric

Dissociation
constant
1.7102
2.05103
1.06103
1.77104
9.3105
6.46105
3.3105
1.8105
1.73105
1.4105
5.3108
1.02107
7.31010

Non-dissociative (real) part, %, at pH


2

37
83.0
90
98.3
99
99.3
99.7
99.8
99.8
100
100
100
100

5.5
32.8
49
85.0
91
93.9
96.8
98.2
98.3
99
100
100
100

0.55
4.65
8.6
36.1
52
60.7
75.2
84.7
85.2
88
95
99.9
100

0.04
0.48
0.94
5.35
9.7
13.4
22.3
35.7
36.6
42
65
99.0
100

0.001
0.049
0.094
0.56
1.06
1.52
2.94
5.26
5.46
6.7
15.8
90.7
100

7
0
0.0049
0.0094
0.056
0.107
0.15
0.30
0.55
0.57
0.71
1.9
49.5
100

Owing to this, molecules of an acid can penetrate into microbial cells, whereas penetration of ions into cells is impossible or barely possible.
As the dissociation constant of a preservative acid decreases, even at a neutral or weakly acidic reaction, the number of non-dissociated molecules, which guarantee its action, increases. The weaker a preservative acid, the closer the pH can be to the neutral point; the
preservative action of the preservative does not decrease. Non-dissociating preservatives,

26

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

e.g., esters of para-oxybenzoic acid, are relatively independent of pH and can change at the
neutral reaction.
1.4.2 Mechanism of action of chemical preservatives
The mechanism of action of chemical preservatives on microorganisms has been little studied to date.
Common methods of determining the inhibitory doses of chemical preservatives can
not reveal the mechanism of their action. They can only establish the concentrations, at
which the propagation of microorganisms slows down. In practice, it is believed that a preservative is efficient if it prevents the growth and propagation of microorganisms.
The probable mechanism of action of chemical preservatives on microorganisms, proposed comparatively recently and accepted at present, is presented below.
Compound

Probable effect

Cationic and anionic surfactants

Disturbance of cytoplasmic cell membrane. Denaturation


of enzyme protein

Phenols, chlorophenols, naphthol


sulfonates, cinnamic acid

Disturbance of cytoplasmic cell membrane. Reaction


with genetic-mechanism proteins

Fatty acids, alcohols and high-molecular- Disturbance of cytoplasmic cell membrane. Competitive
mass aldehydes
inhibition of enzymes by low-molecular-mass acids
Chloroacetic acid

Effect on the cell wall. Competitive inhibition

Benzoic acid, p-chlorobenzoic acid,


p-oxybenzoic acid and its esters

Effect on the cell wall. Competition with coenzyme for


apoenzyme

Salicilic acid

Effect on the cell wall. Competition with nicotinamide


adenine dinucleotide. Competition with amino acids used
by enzyme

Boric acid

Reaction with phosphorus metabolism enzymes

Sulfur dioxide, sodium sulfite, sodium


bisulfite

Reaction with aldehydes formed in dissimilation of


carbohydrates. Reduction of SS bonds in enzyme
protein

Chlorine, chloramines, nitrogen trichloride, peroxides, nitrates and other


oxidants

Breakdown of sulfhydryl groups in enzyme proteins.


Breakdown of sulfhydryl groups in genetic-mechanism
proteins.

Ethylene oxide and other epoxides

Reaction with carboxyl and other active groups in


enzyme protein

Fluorides, fluorosilicon compounds and


fluoroborates

Reaction with prosthetic groups of enzymes. Reaction


with active groups of enzyme protein

Formaldehyde

Reaction with active groups of enzyme protein. Reaction


with active groups of genetic-mechanism protein

Salts

Precipitation of enzyme proteins

Exchange between the bacterial cell and the environment is on the level of a limiting
surface (the envelope); a number of differentiated protoplasmic structures, which create
conditions required for active exchange of the cell with the environment, also occur here.
Any substance violating this topography of the cell causes a disorganization of surface
structures, which is equivalent to cell damage. In these cases, we observe bacteriostasis, or
death, of the cell.

CHAPTER 1

27

Under the action of chemical compounds, the metabolism in the microbial cell changes. Metabolism in any cell is inseparably linked with the activity of the enzymes.
The action of certain chemical substances on some enzymes can lead to the termination
of preparation of nutritive material for assimilation, to the associated lack of nutrients and,
therefore, to the interruption of the growth and propagation of microorganisms, i.e., to a
bacteriostatic effect. If the stores in the cell are depleted, it dies. The total damage of certain
enzymes, in particular, dehydrogenases, can lead to the cessation of the oxidative processes
and associated processes of synthesis, i.e., to the termination of life. Depending on the reversibility or irreversibility of the reaction, the effect will be bacteriostatic or bacteriocidal.
Chemical substances, depending on their specific reactivity, can affect cell enzymes
by interacting with the functional groups of an enzyme. The catalytic action of an enzyme
is determined by several functional groups sulfhydryl, disulfide, indole, imidazole etc.
The breakdown or blockage of a group interacting with substrate or coenzyme leads to the
cessation or deceleration of the catalytic reaction.
The mechanism of blockage of active groups of enzymes can be different. For instance, the sulfhydryl group is blocked via oxidation
2R

SH

R' + H2O.

or substitution of hydrogen
R

SH + R'OH

Formaldehyde is characterized by a small selective reactivity. Depending on pH of the


medium, it can block various functional groups: at pH 9.5, free amino acids; at pH 6.0, the
imidazole group of histidine, at pH 5.0 and lower, formaldehyde is predominantly bound
by amide and guanidine groups; it also reacts with indole and sulfhydryl groups.
The preserving action of sulfurous acid is also based on its capability of damaging the
enzymes of the microbial cell. Substances capable of acting as reducers and oxidizers inhibit the activity of the enzymes. The enzymes containing the functional SS group, on
whose presence their catalytic activity depends, are inactivated by such reducing substances
as SO2, H2S, HCN, dithionate or HCOH. The SS bonds are split to form HS groups.
Besides, sulfurous acids, by reacting with aldehydes formed in carbohydrate exchange, capture them and violate the normal metabolism in the microbial cell. Thus, acetaldehyde sulfonate formed in this reaction is not accessible to corresponding enzymes.
In this case, inhibition of activity of the enzyme system is achieved by blocking the
substrate, which becomes inaccessible to microbial enzymes.
A possible explanation of the mechanism of inhibiting the growth of mold was proposed, proceeding from the supposition that sorbic acid is degraded to final products under
the influence of mold enzymes by the type of the -oxidation of fatty acids. At the same
time, it was established that cyanide selectively inhibits oxidation of butyric acid to -ketobutyric acid under the action of mold enzymes. Dehydrogenase, which catalyzes the conversion of butyric acid to crotonic acid, was not inactivated by cyanide, but the enzyme
system catalyzing the conversion of crotonic acid to -oxybutyric acid, was inactivated totally. This means that ,-unsaturated fatty acids accumulate in the medium; this accumulation inhibits the dehydrogenase system of molds. When sorbic acid is added to a food
product, the final product of the reaction catalyzed by mold dehydrogenase is in excess, and
dehydrogenase can not function.

28

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

At a high mold contamination, the concentration of all enzyme systems increases, owing to which the dehydrogenase activity can not be inhibited. Sorbic acid at a high mold
contamination of a product is not active.
Chemical substances can inhibit an enzyme reaction by acting on a prosthetic group
of the enzyme, by attaching themselves to coenzyme or else to the protein part of the enzyme in such a way that the bond between coenzyme and the protein component of the enzyme (apoenzyme) becomes impossible.
If a chemical substance is similar by its structure to coenzyme, it competes with coenzyme by capturing apoenzyme, as the result of which the enzyme is inactivated. This, in
particular, is one of the mechanisms of action of benzoic acid and its salts, which compete
with coenzyme for apoenzyme. The efficiency of action of benzoic acid in media with a
lower amino acid content is higher than in food products, and under certain conditions nicotinic acid interferes into inhibition by benzoate.
Both inhibition and die-off of microorganisms can depend on various reasons, on one
or several all at once. Therefore, when choosing a preservative, not only its concentration
and time of action should be taken into account, but also the possibility of a simultaneous
damage to a large number of vital mechanisms. To develop preservative formulae with an
extended range of action, one should know the causes of microbial die-off under the action
of a preservative.
As most preservatives possess a specific action with respect to various microbial species, and spoilage of food products is determined by a large number of microbial species,
the development of combined compositions of preservatives has certain advantages. The
additive action of two substances is possible owing to the fact that one substance, by acting
on the cell envelope, facilitates penetration into the cell of another substance, or one of the
preservatives decreases pH, and then the efficiency of action of the other preservative increases.
The efficiency of action of a composition made up from two or more preservatives can
be increased by adding synergists, i.e., the substances, which possess no preservative action
by themselves, but can enhance and maintain the preservative action of a preservative.
Citric, tartaric and malic acids, as well as inorganic acids, their salts etc. can serve as synergists.
The action of double and triple combinations, consisting of a preservative (sorbic,
formic, benzoic acids or para-oxybenzoic acid esters) and an antibiotic (nisin or tylosin, or
both), was studied. A preservative is used to expand the antimicrobial range.

1.4.3 Characteristics and application of chemical preservatives


All methods of increasing the resistance of food products by using chemical preservatives
have their advantages and disadvantages. First of all, taste can become worse, and the nutritive value can decrease. For instance, sulfurous acid degrades vitamin 1 to a significant
extent. Some preservatives are capable of disguising the true quality of a product, and a stale
product can be passed off as a fresh product. For instance, formic acid possesses this capability with respect to meat products. Partially for this reason, preservatives of this kind are
banned in most countries.
Benzoic acid (benzenecarboxylic acid; phenylformic acid) is present in most berries
(0.5%).

CHAPTER 1

29

COOH

Benzoic acid

Benzoic acid is a colourless crystalline substance, difficult to dissolve in water and


rather easily dissolving in ethanol. It is used as a preservative; its efficiency increases in an
acidic medium. The activity of benzoic acid against yeast fungi is higher than against molds.
Sodium benzoate (the sodium salt of benzenecarboxylic acid; the sodium salt of phenylformic acid) is an almost colourless crystalline substance.
COONa

Sodium benzoate

This salt dissolves well in water, worse in ethanol. The preservative activity is exhibited best of all in an acidic medium at pH lower than 5.0.
In studies of acute toxicity of benzoic acid and its sodium salt, LD50 for rats was 2700
mg/kg body weight; for rabbits and dogs, 2000 mg/kg body weight in peroral introduction.
In rats, prolonged feeding of food containing 0.5 and 1% of benzoic acid was found to
have no harmful effect on their growth, fertility and life expectancy. No deviations from
the norm were found in autopsy, either.
The dose causing no significant toxic effect in rats is 1% benzoic acid or sodium benzoate in food, which is equivalent to 500 mg/kg body weight per day.
Benzoic acid is used for preservation of food products usually at a concentration of up
to 0.1%; sodium benzoate, at a concentration not exceeding this amount in terms of benzoic
acid. Though the preservative action of benzoic acid is higher than that of sodium benzoate,
the latter is used more often due to its better solubility in water. The solution should have
pH lower than 4.5, then sodium benzoate is converted into free acid. Already at a 0.1% concentration, sodium benzoate is a strong preservative for many food products. It is efficient
for acidic or slightly acidified products, such as fruit juices, marinaded vegetables.
Benzoic acid and its salts found use mainly for preserving products of plant origin.
In some cases, they are used for preservation of fish products. For instance, in Italy the
use of benzoic acid and its sodium, potassium and calcium salts is permitted for processing
of semipreserved fish products, caviar etc.
Ice containing 0.1% benzoic acid is known to be used for preservation of fish and fish
fillet, and packaging of these products with ice containing 0.150.30% sodium benzoate
enables their storage fresh for several days more than in a packaging with common ice. To
avoid coagulation of fish surface layer proteins, pH of ice is maintained higher than 4.0.
Besides, benzoic acid or its salts added at a concentration of 0.3% to a 5% solution of cooking salt with pH 4.05.0, into which a fish fillet is immersed for 2 min, considerably increases its storage time. Besides, the saline solution improves the taste of fish.
In many countries, benzoic acid and its salts are used for preservation of liquid eggs
and egg yolk.
Sodium benzoate is considered to be a good preservative for oleomargarine. It does
not affect the vitamin content.

30

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Information on the use of benzoic acid or its salts for preservation of meat products is
scarce. Preservation of meat salads and protective gelatin coatings for meat products by
benzoic acid is known to be used.
There are indications that a 0.06% addition of benzoic acid increases twofold the stability of fresh sausages and other meat products. For their longer storage, it is recommended
to add 4 g of a preservative mixture per 1 kg of sausage: 8.5 parts of benzoic acid, 8.5 parts
of sodium benzoate, 8.3 parts of cooking salt. This method significantly inhibits the growth
of all bacterial species.
In Russia, of products having a relation to meat industry, benzoic acid is allowed for
preservation of food gelatin at a concentration of 0.07%.
Methyl, ethyl and propyl esters of p-oxybenzoic acid possess an ability to exhibit a preservative action in a neutral medium.
COOR

OH
p -Oxybenzoic acid ester

In the formula, R is CH3, C2H5 or C3H7.


These esters are colourless crystalline substances with almost no smell. All of them
are hard to dissolve in water and are easily soluble in ethanol.
In acute experiments on mice, LD50 for methyl and propyl esters of p-oxybenzoic acid
was more than 8000, and for their sodium salts 2000 mg/kg of body weight. In similar experiments for the sodium salt of ethyl ester of the same acid, LD50 was about 2500 mg/kg
body weight.
In chronic experiments (96 weeks), methyl ester of p-oxybenzoic acid was introduced
to rats with food in the amount of 2 and 8%. Animals given the feed containing 2% of the
preparation did not differ from controls. In rats, which received feed containing 8% of the
preparation the weight increase went down in the initial period of the experiment, and then
levelled out. Histological studies revealed no significant changes in organs of rats. The
same results were obtained in experiments with propyl ester.
The dose causing no significant toxic effect in rats is a 2% addition of each of the three
esters to food, which is equivalent to a daily dose of 1000 mg/kg body weight.
Esters of p-oxybenzoic acid, mainly ethyl and propyl esters, and their mixtures were
earlier rather broadly used in the West as preservatives for a number of confections marzipan pastes, marmalades etc., mayonnaise, some fish semipreserves, caviar, especially crab
preserves etc. Lately, they are not used in most countries.
In some countries, for instance, Norway, esters of p-oxybenzoic acid and its sodium
salts are permitted to be used at a 0.05% concentration to increase the stability of some fish
semipreserves, special types of cheese, as well as for surface treatment of cheeses. However, before paraffin treatment of cheeses, the preservative should be removed. Preservatives are introduced into compositions containing cellulose esters intended for the surface
coating of salty meat products.
In Italy, ethyl and propyl esters of p-oxybenzoic acid are permitted to be used for preserving semipreserved fish products, caviar, mayonnaise etc. They are used instead of benzoic acid for preservation of meat salads and edible gelatin coatings for meat products.

31

CHAPTER 1

Ethyl ester of p-oxybenzoic acid at a 0.75% concentration makes it possible to store edible
blood without its organoleptic properties changed.
Sorbic acid (1,3-pentadiene-1-carboxylic acid; ,-pentadiene-a-carboxylic acid;
trans-2, trans-4-hexadiene acid) is represented by colourless needlelike crystals with moderately sharp smell:
CH 3CH

CHCH

CHCOOH

Sorbic acid

The technical requirements to edible sorbic acid abroad (in the USA) are as follows:
Melting temperature (dry sample)
Titration (dry sample)
Water content
Heavy metal content
Ash content
Transmission of light (5% methanol solution at 425 m)

133.0137.0C
99.0101.0% (w/w)
3.010.0% (w/w)
1 mg% (maximum)
0.2% (maximum)
95% (minimum) for a layer of 1 cm

Sorbic acid is soluble in cold water only slightly (0.15% at 20C), but is much more
soluble in hot water (3.8% at 100C). The salts of sorbic acid are better soluble in water.
The solubility of sodium sorbate in water is 32%, it does not essentially change depending
on temperature within the range of 060C. The solubility of potassium sorbate is more
than 50% at 20C, and calcium sorbate dissolves in the amount of 1.2% at 25C.
The solubility of sorbic acid in various solvents at 20C is shown in Table 1.3.
Table 1.3
Solvent
Glacial acetic acid
Acetone
Benzene
Carbon tetrachloride
Cyclohexane
Anhydrous ethanol
20% ethanol

Solubility,
g/100 g solvent

Solvent

11.5
9.2
2.3
1.3
0.28
12.9
0.29

Ethyl ester
Glycerol
Cottonseed oil
Anhydrous propylene glycol
25% sodium acetate
15% sodium chloride
Water

Solubility,
g/100 g solvent
5.0
0.31
0.58
5.5
2.1
0.038
0.15

Sorbic acid, having two unsaturated bonds in its structure, is a rather reactive compound. Its autooxidation leads to the formation of peroxides. It should be especially protected from the action of sunlight, otherwise the quality of the crystalline preparation
worsens, which manifests itself in a melting temperature decrease, yellowing and rancidity.
Sorbic acid is used as an antimicrobial substance. It possesses a high activity against
molds and yeast fungi and, to a smaller extent, against bacteria. Its optimal pH is 4.5. The
fungistatic activity increases in the presence of acids and cooking salt. Sorbic acid is found
in berries of mountain ash Sorbus aucuparia L.
In peroral introduction to rats, the lethal dose (LD50) of sorbic acid was 10,500 mg/kg
body weight.
Chronic experiments on rats were conducted for 1000 days on two generations of

32

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

animals. Rats were given feed, which contained 5% of sorbic acid. No deviations in weight
increment and fertility from control animals were observed.
A dose causing no toxic effect in rats is 5% of sorbic acid in feed, which is equivalent
to 2500 mg/kg body weight per day.
In subacute and chronic experiments on animals, sorbic acid was found not only to be
non-toxic but possessed a number of favourable biological properties.
Sorbic acid is used to inhibit the growth of yeasts and against molding of fruit and vegetable juices, marinades, brines, smoked fish, flour confections etc., as well as to prevent
damage of cheeses and margarine by mold. It is also used to impregnate packaging paper
for food products.
Sorbic acid strongly inhibits the growth of molds and yeasts on smoked fish, if
0.050.1% of this preservative is absorbed by fish tissues during their soaking in a brine,
which contains sorbic acid.
Usually, sorbic acid is used at a concentration of 0.020.2% of the weight of a product
and has no influence on its colour and taste within these limits.
In meat industry, sorbic acid did not find wide use; however, there is information that
it is used to inhibit the growth of mold on fermented sausages, for preservation of meat salads and edible gelatin coatings of meat products. A number of studies on the use of sorbic
acid for increasing the stability of meat products yielded positive results.
An aqueous 0.5% solution of sorbic acid was used to remove mold from the surface
of semi-smoked sausages. Wiping and rinsing of sausages in a solution of the acid made it
possible to increase the storage time by 59 days. The loaves wiped with the solution and
kept in it for 15 min could be stored 20 days more than those wiped with water. By adding
0.2% sorbic acid to sausage goods, their storage times can be increased by three days.
Treatment of the surface of raw pork and beef sausages, raw fish fillet, eviscerated
poultry etc. by immersion for 0.12 min into an aqueous solution of 0.15.0% sorbic acid or
its water-soluble salt and up to 0.2% antioxidant impedes microbial and oxidative spoilage.
The treatment of packaged fresh meat by sorbic acid and an antibiotic in combination
with ionizing irradiation is also efficient in inhibiting microbial spoilage.
Deceleration of microbial growth in beef at 2C, achieved by combining ionizing irradiation (105 rad), oxytetracycline (1 mg%) and sorbic acid (0.1%), is shown in Table 1.4.
Table 1.4
Treatment

Control
Irradiation
Oxytetracycline
Sorbic acid
Irradiation + oxytetracycline
Irradiation + sorbic acid
Irradiation + sorbic acid + oxytetracycline

Tenfold population growth, days


yeasts and molds

bacteria

>20
3.59.0
3
>20
4
817
1523

25.5
46
78
35
14
817
1633

However, meat treated in this way is of much lower quality, dehydration is observed,
as well as undesirable changes of colour and decreased flavour.
A promising way of increasing the storage times of eviscerated and cooled poultry carcasses in packagings is a two-stage treatment, which included acid hydration and use of sor-

CHAPTER 1

33

bic acid. Part of a carcass is treated for 2 h in an ice-cooled solution of 2-substituted sodium
phosphate. Herewith, pH < 5.5 is achieved on the surface. Then, after excess liquid leaks
off, the carcass is treated with a hot (70C) solution of sorbic acid. A mixture consisting of
70% propylene glycol, 20% water and 10% glycerine is used as a solvent. The sorbic acid
concentration of 0.11 mg per 1 cm2 of the product surface is achieved in 210 sec of drizzling. Control samples were spoiled in 5 days of storage at 7C, while test samples were
not spoiled in up to 18 days.
In some countries, it is permitted to add 0.1% sorbic acid and its sodium salts, which
are used along with sorbic acid, into animal fats (except butter), margarine, egg yolk or a
mixture of yolk and white. The solubility of the potassium salt in cold and hot water and
wateralcohol mixtures can be considerably decreased in the presence of cooking salt and
saccharose. They are active at pH 6 and lower.
Methods of commercial synthesis of sorbic acid have been developed in this country
to date. Sorbic acid possesses a high efficiency with respect to molds and yeasts.
Sulfur dioxide (SO2), sodium sulfite (Na2S03), sodium metabisulfite (Na2S2O5), sodium bisulfite (NaHSO3) are soluble in water and are used as antimicrobial substances, as well
as for preventing the browning of food products.
In acute experiments on mice at the intravenous injection, LD50 was 130 mg/kg body
weigh for sodium bisulfite and 175 mg/kg for sodium sulfite.
Chronic experiments were performed in several groups of rats, 1824 animals in each
group. The daily ration given to rats for 12 years included sodium bisulfite in the amount
of 0.0125, 0.025, 0.05, 0.1, 0.25, 0.5, 1 and 2% of the feed. No toxic phenomena were found
in rats given 0.05% sodium bisulfite for 2 years.
Addition of sulfite to the feed at concentrations of 0.1% or higher caused growth inhibition in rats, possibly as the result of the degradation of thiamine in the feed.
The dose causing no significant toxic effect in rats is 0.05% sodium bisulfite in the
feed, which is equivalent to 15 mg/kg body weight per day in terms of sulfur dioxide.
Sulfur dioxide found wide use for preservation of fruits, juices etc., but its application
for products of animal origin is very limited. In Russia, this preservative is permitted to be
added into food gelatin. The content of sulfurous acid in dry product should not exceed
0.1%.
In Norway, the content of sodium bisulfite in vacuum-packaged salt fish fillet is permitted to be up to 0.14%.
In England, sulfur dioxide is permitted to be used for preservation of raw sausages in
the amount of 45 mg% of the weight of a product. In Scotland this addition of sulfur dioxide
is permitted for chopped raw meat for the three summer months.
The treatment of sausage filling with sodium metabisulfite (in terms of 0.5 g SO2 per
kg of filling) increases its storage time at 5C 2- or 3-fold. One of the undesirable phenomena in SO2 treatment is, as was pointed out earlier, a considerable degradation of vitamin B1.
It has been proposed to treat the surface of hen and duck carcasses with metabisulfite.
Carcasses are to be immersed into a bath with a 1% metabisulfite solution at a temperature
of 6366C and be held for 1 min. Then the carcasses are dried on a dressing rail and packaged into boxes. The treated carcasses are stored 35 times longer than controls at 810C.
A method was recommended to preserve gut raw material using a 0.5% solution of
metabisulfite. The method is of particular importance for enterprises located in the thermal
belt or those that prepare guts for long-time storage and transportation. Thus, a six-month
storage of beef casings, bungs, rounds, hog and sheep casings as raw materials at a temper-

34

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

ature of 1524C and beef, hog and sheep casings as semifinished products at 2940C did
not lead to any deviations from the norm during the subsequent use in sausage production.
To preserve non-food raw material and condemned materials (from non-infected animals), not processed by meat-processing plants for dry animal feeds in the period of mass
livestock dressing, it is recommended to add dry sodium or potassium pyrosulfite
((Na2S2O5 or K2S2O5) in the amount of 2% of the weight of raw materials.
The same preservatives are proposed to be used for preservation of blood intended for
feeding, which was earlier preserved by potassium oxide or diluted sulfuric acid in the presence of cooking salt. Defibrinated blood preserved using 1% potassium pyrosulfite to the
weight of the blood can be stored for two months in the summer time at room temperature.
In gelatin production, sulfurous acid or hydrogen peroxide or both substances consecutively are usually used for preserving and whitening of high-quality broths intended for
producing photographic gelatin.
For preservation of glue, a number of preservatives are used, including sulfur dioxide
and sodium bisulfite.
Aliphatic acids. Fatty acids containing from 1 up to 14 carbon atoms are efficient inhibitors of molds. Propionic acid and its sodium and potassium salts prevent molding of
bread and baked products. Salts of propionic acid found use in dairy industry, in particular
in preventing molding on some types of packaged cheeses.
In meat industry, propionic acid and its salts found no use, because they deteriorate
the organoleptic properties of meat products. However, it is possible that further research
in this direction would find a possibility of using propionic acid and its salts for mold control in sausage production.
Formaldehyde, formic acid, salicilic acid, boric acid, borax, mono-, di- and trichloroacetic acids, hexamethylene tetramine (urotropin) etc. found application as food preservatives. At present, their use is banned in most countries, but in some countries hexamethylene
tetramine, formic and boric acids are still permitted to be used for preservation of caviar
and other fish products.
1.4.4 Methods for identification of preservatives
Quantitative determination of preservatives in products is made by gravimetric, titrometric,
spectrophotometric, chromatographic and other methods.
A number of methods have been proposed for determining the content of sorbic acid
in products. In most of them, the acid is isolated from a product by steam distillation. The
distillate is used for the assay directly or is used to extract sorbic acid with ether to reduce
the effect of minor impurities present in the distillate. In some cases, sorbic acid is isolated
by extraction. However, this method is not applicable for fats and products containing large
amounts of fat.
In the distillate or extract, sorbic acid can be determined titrometrically.
A simple method is the iodometric determination of sorbic acid in distillates or extracts
from margarine, dairy products etc. The error of the method is 2.25.0%.
The widespread spectrophotometric method of determining sorbic acid in products is
based on the ability of sorbic acid solutions to absorb light in the ultraviolet region of the
spectrum. The light absorption maximum of the solution at pH 5.9 corresponds to the wavelength of 256 m, and at pH 4.0, 262 m.
The spectrophotometric method of determining sorbic acid, developed for cheese, was
applied for other food products (bread, cakes, syrups, meat produces etc.).

CHAPTER 1

35

Later, a more precise spectrophotometric method was recommended.


The content of sorbic acid in margarine was determined by the light absorption in the
ultraviolet region of the spectrum at 260 m.
The basis of one of the spectrophotometric methods is the reaction of sorbic acid with
2-methyl-mercaptobenzthiazol-p-ethyl toluene sulfonate (benzthiazol), which leads to the
formation of a green product, whose light absorption is measured at a wavelength of
652 m. Other chemical preservatives benzoic, sulfurous, salicilic, formic, cinnamylic,
propionic acids and a mixture of p-oxybenzoic acid esters give no green coloration with
benzthiazol and do not prevent the determination of sorbic acid. The method is recommended for determining sorbic acid in food products (cheese, butter etc.).
The method of paper chromatography was proposed for determining the content of
preservatives in bread and baked products. Formic, propionic, benzoic, salicilic, sorbic,
p-chlorobenzoic, p-oxybenzoic acids and p-oxybenzoic acid esters were identified.
For separation of p-oxybenzoic acid and some of its esters, methods of paper chromatography were also described, but they are lengthy and are inferior to thin-layer-chromatography methods in this respect.
The method of thin-layer chromatography was successfully used to separate p-oxybenzoic acid and its methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, heptyl, octyl,
nonyl, dodecyl, phenyl and benzyl esters. A mixture of 10% acetylcellulose and polyamide
(1:1, w/w) was used as the stationary phase; a two-component system consisting of a
hydrocarbon solvent and glacial acetic acid (50:10, v/v), as a mobile phase.
The separation of methyl and propyl esters of p-oxybenzoic acid was achieved on a
thin layer of silica gel using a mobile phase from a mixture of pentane and glacial acetic
acid.
A major part of the methods of determining sulfurous acid is based on its capability of
being readily oxidized. There are volumetric and gravimetric method of determining sulfurous acid.
A comparatively exact and fast assay is the iodometric method of determining sulfur
dioxide using formalin, which binds sulfurous acid.
1.4.5 Fat antioxidants
Under the action of oxygen of the air, fats undergo oxidative processes, which even at the
early stages are accompanied by a decrease of nutritive value and subsequently lead to
spoilage (unpleasant odour and taste, sometimes change of colour and consistency of fat).
The modern views on the mechanism of oxidative reactions of organic substances are
based on the BachEngler peroxide theory and the theory of degenerate branched chain reactions by N.N. Semenov.
In accordance with the peroxide theory, the first product of oxidation of most organic
and many inorganic substances are peroxides. When peroxide is formed, two atoms of the
oxygen molecule still remain bound to each other. Therefore, in the oxygen molecule there
is no complete rupture of bonds between atoms, which would require a large consumption
of energy (117 kcal/mol). Thus, oxidation of organic substances via peroxide formation
proceeds comparatively easily.
Peroxides were found even in freshly produced fats, because their oxidation begins already at the technological processing: in preparation of raw fat for rendering, during the rendering and in subsequent operations. Formation and accumulation of peroxides is greatly
affected by the method of rat production. Comparison of the results of peroxide numbers

36

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

determination for pork rendered fats, obtained by various investigators, shows that the peroxide numbers of a fat rendered in an open heater are 0.0130.035, and for that rendered
on a centrifugal machine, 0.0000.025.
The chemical composition of initial raw material and the changes that occurred in technological processing determine subsequently the rate of spoilage of fats in storage. The
spoilage rate of a fat present in food products also depends to a great extent on these factors.
Many investigators, in particular, by the example of oxidation of fatty acid esters, have
convincingly shown that at least at the first stages of oxidation all peroxide products formed
are hydroperoxides
R1

CH

CH

CH

R2

OOH

In the formation of hydroperoxide, oxygen attacks the CH bond at the -position to


the double CC bond, which possesses an increased reactivity in oxidation processes. Abstraction of the -methylene atom H from the compound containing double bonds between
carbon atoms leads to the formation of active free radical CHCH=CH, which requires
an energy consumption of about 80 kcal/mol. This energy is required in the onset of the reaction for breaking the CH bonds. The further development of the reaction by the chain
mechanism requires a very small amount of energy or no energy at all.
It has been proven experimentally that with the abstraction of the hydrogen atom the
double bond is not broken, but that this phenomenon is accompanied by the displacement
of double bonds in fatty acid molecules. Herewith, coupled double bonds
C

appear in the molecules of polyunsaturated fatty acids (containing two or more double
bonds), which initially contained only isolated double bonds.
The possibility of the presence of cyclic peroxides
R1

CH

CH

R2

in oxidation products has not been proven to date by direct methods. While hydroperoxides
were isolated and studied, cyclic peroxides were not, possibly because of their extreme instability or because they do not exist. In most cases, the proof of the emergence of cyclic
peroxides at the advanced stages of oxidation is based on the determination of the general
content of peroxide compounds by the iodometric method and the determination of only
hydroperoxides by the polarographic method. However, the quantitative differences obtained are within the limits of error of the determination methods.
Hydroperoxides are comparatively unstable compounds easily undergoing various
conversions, which lead to the rupture of the OO bond and the formation of free radicals.
The bond rupture energy in peroxides is considerably lower than in the oxygen molecule
and makes 3040 kcal/mol. As the result of dissociation or other conversions of peroxides,
the system forms more stable oxidation products as compared with peroxides the so called
secondary oxidation products aldehydes, ketones, low-molecular-mass acids etc. While
hydroperoxides have no smell or taste, many of the secondary oxidation products of relatively low molecular masses are involved in the formation of a specific smell and taste of
spoiled fats.
The quantum yields determined in photochemical oxidation prove to be much larger

CHAPTER 1

37

than unity (according to Einsteins law of photochemical equivalence, one quantum of light
induces only one chemical reaction), which is a direct proof of the chain nature of the oxidation reactions.
Other proofs of the chain mechanism of the oxidation processes can be the phenomena
of initiation (excitation) and retardation (inhibition) of the oxidation reactions. In the former
case, oxidation is accelerated in the presence of substances capable of decomposition into
free radicals; in the latter, of being inhibited by addition of minor amounts of substances
capable of interrupting the chain reaction of oxidation by capturing free radicals that lead
the oxidation chain. Oxidation of fats proceeds via formation of free radicals and pertains
to the class of slowly evolving chain branched reactions.
Free radicals are highly active particles. Reactions between free radicals and between
free radicals and molecules proceed easily; new free radicals are formed in the process to
continue the chain reaction.
It is well known that the smaller the activation energy E, the easier the reaction between two reacting chemical compounds is. If two molecular compounds participate in the
reaction, the magnitude of the activation energy is usually several tens of kilocalories per
mole. In the case of the reaction of free radical with a molecule, the magnitude of the activation energy is not large or equals zero, i.e., E is within the range of 010 kcal/mol.
Besides the reaction product (in this case, hydroperoxide), a new free radical (R) is
formed in the chain reaction mechanism. This radical again enters into the reaction and continues the initiated chain of chemical conversions. Herewith, more new molecules of the
initial substance are involved into the oxidation reaction. Thus, the development of the oxidation chain occurs and the involvement of new molecules of the fatty acid or triglyceride.
The chain of oxidative conversions develops until the chain-leading free radicals R
and RO2 disappear from the system, i.e., as the result of recombination of two radicals. An
inactive compound is formed, and the chain terminates. The sooner this happens, the less
fatty-acid or triglyceride molecules get oxidized.
Occasionally, the molecular product of the chain reaction in the system where the oxidation process occurs hydroperoxide breaks down to form new free radicals, i.e., the
chain branches, as each newly formed free radical initiates a new oxidation chain.
The slow development of the oxidation reactions is due to the fact that the branchings
of the chain in these reactions are as if retarded and occur only at times when hydroperoxides break down to free radicals. These retarded branchings are called degenerate
branchings.
Below, we present a generally accepted scheme of a degenerate branched chain
reaction:
RH + O2

R + HO 2

R +O
RO 2
RO 2 + RH
RO2H + R
RO2H
RO + OH
RO 2 + RO2
R +R
RO 2 + R

Chain initiation (formation of free radical R)


Chain continuation
Degenerate chain branching
Chain termination

Here RH is the molecule of an oxidizing substance, e.g., a fatty acid; RO2H is the
hydroperoxide molecule; R and RO2 are free radicals leading the oxidation chain; RO and
OH are free radicals formed in the breakdown of the hydroperoxide.

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Peroxide numbers, % iodine

38

0.5
0.4
0.3
0.2
0.1
0
0

10
Time, h

15

20

25

Figure 1.2 A kinetic curve of peroxide accumulation in oxidation of pork rendered suet. Oxidation
temperature, 90C.

The slow development of fat oxidation in the initial stage is due to the delay of chain
branching. This stage of oxidation is known under the name of the induction period or
initiation period.
However, at later stages of oxidation, when a large amount of free radicals accumulate
in the system, the oxidation process is sharply speeded up. The typical autocatalytic character of the kinetic curves for oxidation of fats and related substances is clearly seen by the
example of the oxidation of pork rendered fat.
The ability of hydroperoxides to break down to form free radicals, as well as the dependence of the oxidation rate on the extent of oxidation in the cases when hydroperoxides
are basically the only reaction products, indicates that degenerate branching in liquid-phase
oxidation reactions is due to the breakdown of hydroperoxides in the reaction
ROOH

RO + OH or 2ROOH

RO 2 + RO + H 2O .

Below, we will show that oxidation of both melted and solid animal fat proceeds according to the same kinetic law.
The rate of fat autooxidation is commonly characterized, not only in research but also
in practice, by the length of induction period, i.e., the length of time during which no pronounced changes in them are observed. This period serves as a preparation to fast oxidation.
In the beginning of the induction period, there is no sign of any oxidation products accessible to chemical determination, then peroxides start to be found, and at their sufficient
amount, due to the autocatalytic character of the process, oxidation begins to develop at a
very high rate, the induction period ends. Upon completion of the induction period, the peroxide accumulation curve sharply rises (see Fig. 1.2).
It should be pointed out that, in an ideal representation, the induction period should be
understood to be only that part of the segment of the curve in which peroxides are not found
by common chemical (or physicochemical) methods. In practice, in modern production processes, it is difficult to obtain fat not containing peroxides found analytically. In the main,
freshly produced fats always contain peroxides in minor amounts. Therefore, for practical
purposes a more suitable definition of induction period is that, which is given initially. It is
all the more correct as the notion of induction period is conventional, because oxidative
changes not registered by chemical methods are observed in fats in the cases when the presence of peroxides is not yet possible to detect by common analytical methods. It is known

Peroxide numbers, % iodine

CHAPTER 1

0.5

0.4

39

0.3
0.2
0.1

8
10
Time, h

12

14

Figure 1.3 Kinetic curves of accumulation of fat samples taken at different stages of the technological process (oxidation temperature, 100C): 1, after rendering; 2, from the collector; 3, from a
container.

that hydroperoxides at a concentration of 10 6 mol/l can not be found by common chemical


methods.
At the same time, the kinetic methods make it possible to register changes in fat at very
early stages of oxidation. Studies of fat samples taken from the same commercial batch at
different stages of the technological process and containing no peroxides determinable by
the iodometric method (peroxides were found in none of the samples) showed that the stability of fat to oxidation as determined by the kinetic method (Fig. 1.3) was different.
Secondary oxidation products include comparatively stable intermediate and end
products of oxidation alcohols, carbonyl compounds, esters, acids, as well as compounds
with mixed functions, such as oxy acids, epoxy compounds etc.
It could be said that all secondary products of oxidation emerge as the result of conversions of hydroperoxides; what is more, part of the secondary products are formed immediately at the breakdown of hydroperoxides and the other part, as the result of further
reactions.
The primary character of hydroperoxides as the first molecular products of oxidation
and the secondary character of carbonyl compounds, alcohols, epoxy compounds and acids
is graphically illustrated by curves plotted based on the literature data on the oxidation of
methyl oleate under the action of ultraviolet light at 35C (Fig. 1.4).
The mechanism of formation of secondary oxidation products has been little studied.
Only with a small fraction of probability, it could be suggested that ketones are formed from
hydroperoxides:
R1 CH R 2 + R
R1 C
R2 + RH
OOH
R1

C
OOH

OOH
R2

R1

R2 + OH ,

where R is either radical OH or any of the radicals leading the main chain of oxidation.
It is probable that alcohols are formed from hydroperoxides in degenerate branching
of chains

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

nmol O2 / 100 g nonvolatile


oxidized substrate

40

50

2
4

5
0

100
Time, h

200

Figure 1.4 Kinetic curves of oxidation of methyl oleate at the action of ultraviolet light: 1, peroxide
oxygen; 2, carbonyl oxygen; 3, hydroxyl oxygen; 4, oxirane oxygen; 5, carboxyl oxygen.

ROOH

RO + OH

RO + RH

ROH + R

One of the possible routes of forming epoxy compounds is the intramolecular reaction
of the hydroperoxide of the unsaturated compound
R1

CH

CH

CH

R2

R1

OOH

CH

CH

OH

CH

R2

According to one of the most probable points of view, acids can be formed from ketones by their oxidation to -ketohydroperoxide, which subsequently breaks down to form
aldehyde and acid
H
R1

C
O

CH2

R2

R1

CH

OOH

R2

R1C
O

OH + R2

C
O

It has been proven experimentally that acids are not formed directly from hydroperoxides and emerge as the result of the further conversion of secondary oxidation products,
most probably, ketones. As seen from the above reaction, formation of acids proceeds with
the rupture of the carbon skeleton of the molecule. Studies of the composition of the acids
formed in oxidation of fatty acids and hydrocarbons confirm this, because in practice only
acids with a shorter carbon chain than in the initial compound could be isolated from the
oxidizing mixture.
The described mechanisms of formation of secondary oxidation products are basically
hypothetical and were proposed mainly based on the studies of hydrocarbons of the olefin
and paraffin series. However, they can be accepted with an equal degree of probability for
oxidation of fatty acids.
This can be done based on that in such acids being part of fats as, e.g., oleic, linolic or
linolenic acids, oxidation at the initial stages affects carbon atoms removed from the ester
group by a chain of at least six methylene groups. Therefore, the ester group can have no
influence on the oxidation process, and oxidation proceeds the way it does in the respective
unsaturated hydrocarbon.

CHAPTER 1

41

mol O2 / mol ester

1.0
0.8
0.6

0.4
0.2

1
100

50
Time, h

Figure 1.5 Dependence of the rate of oxidation of fatty acids in the air at a temperature of 37C on
the number of double bonds in them: 1, ethyl oleate; 2, ethyl linoleate; 3, ethyl linolenate; 4, methyl
arachidonate.

mol O2 / mol ester

1.0
0.8
0.6

0.4
0.2

1
100

50
Time, h

Figure 1.6 Kinetic curves of oxidation of pork suet at different temperatures: 1, 90C; 2, 100C; 3,
110C; 4, 120C.

Products of oxidation of fats and oils, as well as fatty acids and their derivatives are
found to have oxidation products belonging to the same groups of organic compounds,
which were found in hydrocarbons of the olefin and paraffin series, i.e., alcohols, carbonyl
compounds, epoxy compounds, acids etc.
For instance, carboxyl compounds of oxidized fats identified by chromatographic,
spectrophotometric and other methods include n-hexanal, 2,4-decadienal, propionic aldehyde, 2-hexanon, 2-octanon, 2-nonanon, 2-decanon, n-pentenal, acetaldehyde etc.
The reactivity of fatty acids increases with the increase of the number of double bonds
in the molecule. Figure 1.5 shows a dependence of the oxidation rate of unsaturated fatty
acid esters on the number of double bonds.
Formation of free radicals in the system is facilitated with the temperature increase.
Herewith, the chain initiating rate and, therefore, the oxidation rate, increases. Kinetic
curves of pork fat oxidation illustrating this are presented in Fig. 1.6.
If chain initiation occurs mainly according to the reaction RH + O2, then the rate of

42

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

mol O2 / mol ester

1.0
0.8
0.6

0.4
0.2

1
100

50
Time, h

Figure 1.7 Effect of oxygen pressure on the rate of oxidation of ethyl linoleate at 45C.

initiation should depend on oxygen pressure. The occurrence of this dependence at small
conversion rates has been established in oxidation of ethyl linoleate. From Fig. 1.7, it follows that the rate of ethyl linoleate oxidation on oxygen pressure becomes pronounced at a
pressure less than 200 mm Hg. However, it should be noted that the pressure range in which
a pronounced dependence of the oxidation rate on oxygen partial pressure is still pronounced can change within broad limits in transition from one compound to another.
Processes of oxidative spoilage of fats, as well as other chain reactions, are also affected by light and ionizing radiation, which contribute to the emergence of free radicals in the
system.
The action of light of certain wavelengths and especially UV light on fats increases
the rate of emergence of free radicals, which leads to a fast oxidative spoilage of fats.
In the use of ionizing radiations to increase the stability of meat and meat or other food
products in storage, the most serious negative consequence of irradiation is oxidation of
fats. The emergence of free radicals in the presence of oxygen leads to the formation of peroxide radicals RO2 and, therefore, peroxides and products of their conversion.
Variable valence metals iron, copper and others, which get into fats from the equipment in their processing, are efficient catalysts of oxidation processes.
The catalytic acceleration of the oxidation reactions by these metals is based on that,
depending on the valent state, they can either attach an electron or donate it to any valent
saturated particle, which leads to the activation of radical breakdown of hydroperoxides according to the following mechanism:
ROOH + Fe2+

Fe3+ + RO + OH

ROOH + Fe3+

Fe2+ + ROO + OH+

Iron is not consumed in this process and, therefore, being present as traces, it contributes to the emergence of radicals RO and RO2, which initiate the chain process of oxidation. By the example of metal-catalyzed oxidation of methyl linoleate, it has been shown
that metals accelerate the oxidation process only in the presence of the peroxides of oxidized material or of specially added peroxides.
From literature data, it follows that lead has the largest catalytic efficiency, which is
followed by copper, iron, tin, zinc and, finally stainless steel.
Traces of metals contribute to spoilage of animal fats, which is called tallowiness. In
practice, tallowiness is observed, e.g., in excessive intensive mechanical treatment of fats,

CHAPTER 1

43

owing to a lengthy contact with metal apparatuses or long-time storage of fat in a metal container. Tallowiness occurs without a significant accumulation of peroxides. The main oxidation products in this case are oxy acids and, possibly, polymerization products.
The catalytic activity of variable-valence metals increases considerably if they enter
into the reaction with some specific organic compounds, especially proteins.
Meat and blood pigments myoglobin and hemoglobin, as well as their derivatives are
strong catalysts of oxidation of lipids of meat, meat products, fatback.
This, in particular, is confirmed by the acceleration of linoleate oxidation in the presence of extracts of hog muscle tissue. Coagulation of proteins considerably decreases the
catalytic activity of meat pigments. Hemoglobins of different animals differ insignificantly
by their catalytic action on the process of linoleate oxidation.
A decrease of temperature contributes only moderately to the decrease of the rate of
oxidation catalyzed by meat and blood pigments.
Fresh meat pigments, as well as their derivatives are nonspecific catalysts, e.g., hematin also contributes well to oxidation of hydrocarbons and also fatty acids.
Though fat oxidation catalyzed by heme compounds has been known since long, the
mechanism and chemistry of this process have not been made clear until now, possibly owing to the exceptional complexity of this phenomenon.
There is no doubt that both forms of iron (Fe2+ and Fe3+), which are components of
heme compounds, initiate the breakdown of hydroperoxides and, thus, accelerate oxidation
of fat. But there is also no convincing proof that the Fe3+-containing pigment is capable of
accelerating oxidation of lipids in the absence of hydroperoxides, though, according to the
literature data, this is believed to be possible.
The presence of oxidation products in fats is revealed, as well as the extent of the oxidation process is assessed by using chemical, spectrophotometric, chromatographic, polarographic etc. methods.
Methods of determining compounds of peroxide character have become widespread.
Especially frequently, the iodometric method of determining peroxides is used. The
ironrhodanide, indophenol, ironchlorideindophenol, polarographic, stannochloride
etc. methods are used more rarely.
The content of peroxides in edible fats and oils, as well as in food products is expressed
in different way. In the Russian Federation, it is accepted to express the content of peroxides
in percent iodine; in the UK, in millilitres of a 0.002 N solution of thiosulfate per gram of
fat (Lee number). In the USA, the peroxide content is expressed predominantly in milliequivalents or millomoles of active oxygen of peroxides per 1000 g of fat.
There is a certain dependence between the magnitude of the peroxide number and the
organoleptic rating of the quality of fats and fat-containing products, because peroxides in
them accumulate in parallel with the emergence and development of rancid smell and taste.
In fatty tissue separated from a freshly killed animal, it is impossible to find fatty peroxides, because they are not a normal metabolic product in the animal organism. However,
fatty peroxides can be formed in the organism of the alive animal in pathological cases, e.g.,
under the action of ionizing radiation.
As we pointed out, peroxides emerge in fat during the technological treatment and storage. Delays of the raw materials before rendering, high temperature, the presence of atmospheric oxygen, the contact with metal equipment, long-time treatment, effect of light,
incorrect condition of storing the final product all these contribute to the emergence and
further accumulation of peroxides in fat.
The relation between the organoleptic evaluation of the extent of fat spoilage and the

44

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

content of peroxide compounds in it has been discussed in the literature over a period of
many years. Investigators proposed various values of peroxide numbers, which, in their
opinion, corresponds to organoleptically established spoilage.
The values of peroxide numbers characterizing the extent of oxidative spoilage of animal rendered fats are in most cases inapplicable for assessment of the extent of oxidative
spoilage of other types of fats and oils, as well as fat-containing products. While the peroxide number of 0.1 in percent iodine, as a rule, indicates that the spoilage of pork, beef, mutton and bone rendered fats did occur, the same magnitude of the peroxide number for
fatback, vegetable oils and many fat-containing products, including meat products, will be
organoleptically assessed as good-quality foodstuffs.
Methods of determining carbonyl compounds in autooxidizing fats are of great importance, as, on the one hand, the presence of these compounds indicates the extent of oxidation
and, on the other hand, testifies the development of rancid taste determined organoleptically. It is commonly accepted that aldehydes and ketones, together with low-molecular-mass
acids, are a cause of rancid smell and taste. Heptyl, nonyl, hexyl and butyl aldehydes have
long been referred to as substances, which determine rancid smell and taste of fats.
An unpleasant smell of meat and meat products formed under the action of ionizing
radiations depends to a significant extent on the presence of carbonyl compounds.
Carbonyl compounds in oxidized fats and those that are components of meat, meat
products and other food products are determined by methods based on the conversion of
carbonyl compounds to their bisulfite, hydroxylamine, diphenylcarbazide, 2,4-dinitrophenylhydrazine and other derivatives. The methods using 2,4-dinitrophenylhydrazine are the
most widespread. The formed 2,4-dinitrophenylhydrazones of monocarbonyl compounds
and corresponding osazones of dicarbonyl compounds are converted, by addition of alkali,
into intensively stained quinoid compounds, whose light absorption is measured. Separation of the mixtures of carbonyl compounds into classes or individual compounds is done
by methods of column, thin-layer, paper and gas chromatography.
The reaction with 2-thiobarbituric acid is used in determining such a product of oxidative spoilage of fats as malonic dialdehyde.
The content of ,-dicarbonyl compounds, which are characterized by stability in
heat treatment of fats, is determined by treating the fat under study by alkali during the heating. Then the fluorescence or light absorption of the solution is measured.
Epoxy compounds, which were found to emerge in pork fat only in utmost stages of
oxidation, are determined using methods of splitting the oxirane ring with anhydrous hydrogen chloride in absolute ether or with hydrogen bromide in glacial acetic acid followed
by titration with excess hydrogen chloride or bromide. A method of determination by trimethylamine hydrochloride was also described.
More detailed information on the methods of quantitative determination and identification of products of oxidative spoilage of fats can be found in a number of literature sources, which contain references to original papers.
1.4.6 Effect of oxidation on the food value of fats
In long-time storage of fats their quality deteriorates, which leads to a decline of category
quality (in some cases, edible fats are transferred into the technical-grade category) and related material damage. The terms of refrigerator storage of frozen meat depend primarily
on oxidation of fats. Fat oxidation often affects the quality of long-stored smoked sausages,
fatback, as well as fat-containing dried meat and concentrated feeds.

45

CHAPTER 1

However, considerably earlier, long before oxidation can be detected organoleptically,


the food value of fats begins to decrease. As the action of oxygen of the air affects easiest
of all the unsaturated components of fats, the first to get oxidized are polyunsaturated fatty
acids vital for the human and animal organism. Essential polyunsaturated acids are linolic,
linolenic and arachidonic acids. All these natural acids have a cis-configuration. All of them
have a strong biological action, owing to which they are united under the name of vitamin F.
Of polyunsaturated acids, arachidonic acid has the largest biological activity. It occurs
only in lipids of animal origin. Linolic and linolenic acids are synthesized by plants. In the
animal organism, they are capable of converting into arachidonic acid.
Linolic and linolenic acids are contained in large amounts in vegetable oils. Of animal
fats, considerable amounts of linolic acid occur in pork fat.
The data on the content of polyunsaturated fatty acids in fats of slaughter cattle are given in Table 1.5.
Table 1.5
Product

Rendered pork fat


Pork fatback
Fat of salted cooked ham
Rendered beef fat
Rendered mutton fat
Bone fat
Rendered camel fat
Rendered horse fat

Content of acid, %
linolic

linolenic

arachidonic

Number of
samples
studied

9.940.72
11.221.24
10.002.35
2.810.50
3.090.61
4.130.96
4.320.14
11.771.74

0.570.15
0.660.22
0.620.26
0.630.18
0.920.14
0.910.15
1.480.10
5.381.91

0.620.16
0.630.35
0.670.25
0.110.03
0.100.03
0.140.01
0.390.02
0.260.01

11
38
15
7
4
4
4
4

The absence of polyunsaturated fatty acids in the food of rats was found to lead to dermatites, loss of weight, interruption of growth, loss of hair; affection of kidneys, mammary
glands and other organs. At a prolonged insufficiency of vitamin F, animals die. A timely
delivery of polyunsaturated fatty acids into the organism protects animals from death.
As we have already pointed out, autooxidation of fats leads to the formation of hydroperoxides and a related displacement of double bonds. Unsaturated fatty acids with conjugated double bonds, e.g., 9,11-octadiene acid, possess no biological activity.
Along with a decrease in the amount of polyunsaturated fatty acids in autooxidized
fats, the content of fat-soluble vitamins A and E decreases. In coloured animal fats, provitamin A carotene breaks down. If oxidation affects the fat being in contact with meat
and blood pigments (myoglobin, hemoglobin) or their derivatives, then the B-complex vitamins thiamin, riboflavin, pyridoxine, biotin etc. also break down.
The food value of fats decreases not only in long-time storage, but also in heat treatment. Profound chemical changes have been established to occur in heat treatment of fats:
formation and breakdown of peroxides, formation of compounds with conjugated double
bonds, increase in the content of free fatty acids, decrease of iodine numbers, increase of
viscosity, formation of epoxy compounds etc.
Many investigators have proven the harmful effect of oxidized fats on the animal organism. This issue is dealt with in numerous reviews. Intensive research is under way in
this field. For instance, it has been found that feeding chickens small amounts of oxidized
animal fat leads to the retardation of growth and sexual development. Substances isolated

46

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

from the unsaponifiable fraction of oxidized beef fat were found to cause chicken diseases
(ascites, hydropericardium, oedema) at their amounts of 10 5 106% in food.
Some authors postulated a relationship between the activity of various enzymes and
their sulfhydryl groups. In living organisms, these groups are associated with the functions
of muscle contraction, nerve activity etc. Inhibition of sulfhydryl groups of enzymes by lipid peroxides has also been postulated.
It has been experimentally found that SH groups of cysteine, glutathione and also papain get totally oxidized in the presence of linolic acid peroxides.
It is believed that the harmful effect of oxidized fats on the organism is determined
mainly either by their direct toxic effect or by the degradation of vital components of food
they cause due to oxidation. There is no common point of view on this issue yet, and it is
still debated in the literature.
The toxicity of hydroperoxides isolated in pure form was established by direct experiments. Besides, it is known that inclusion of more than 1% rancid fat into the ration of piglets leads to the development of symptoms of vitamin E insufficiency. Inclusion of oxidized
(at 180C) soybean oil into the ration has the same effect as insufficiency of vitamin E, and
leads to the decrease of the content of polyunsaturated fatty acids in organs and tissues of
animals, which stipulates the vitamin E insufficiency.
Thus, there is no doubt as to the harmfulness of oxidized fats both as the consequence
of the loss of food value and of the accumulation of oxidation products which inflict harm
to the human and animal organism.
1.4.7 Inhibition of autooxidation processes
The oxidation reaction, as any chain reaction, can be inhibited by adding inhibitors, in this
case oxidation inhibitors, or antioxidants.
Antioxidants inhibit the chain process of oxidation by entering into reaction with free
radicals RO2 or R and, thus, break the oxidation chains.
Schematically, the mechanism of action of antioxidants can be presented as follows:
InH + RO 2

RO2H + In ,

where InH is antioxidant; RO2 is free hydroperoxide radical; RO2H is hydroperoxide of,
e.g., a fatty acid, In is free radical of the antioxidant.
As a consequence of the principle of the indestructibility of free valence, a new free
radical emerges from the antioxidant, but this radical possesses a very small activity and is
not capable of participating in chain continuation. The reaction is broken, and oxidation is
inhibited. The free radical enters into the recombination reaction with other low-active free
radicals to form a stable product, In + In In In.
Herewith, one molecule of antioxidant is consumed for each chain-breaking act, and,
therefore, its concentration constantly decreases in the process of oxidation. After all inhibitor is consumed, the chain process is resumed and will develop at almost the same rate as
before the inhibitor was introduced.
Figure 1.8 presents kinetic curves characterizing the accumulation of peroxides in pork
fat with an antioxidant and the decomposition of the antioxidant as the result of oxidation.
Another reaction of the death of low-active free radical In is possible in the case of its
emergence from substances of phenolic nature. If the concentration of free radicals RO2 or
R is large, they can interact with low-active free radicals of the inhibitor

0.30

0.25

25

0.20

20

0.15

15

0.10

10
2

0.05

5
0

8 10 12
Time, h

14

16

47

Content of antioxidant, mg %

Peroxide numbers, % iodine

CHAPTER 1

18

Figure 1.8 Kinetic curves, which characterize accumulation of peroxides in pork fat with an antioxidant and its breakdown as the result of oxidation at 110C: 1, peroxide numbers; 2, content of
butyloxytolyene.

In + RO 2

InRO2

or
In + R

InR.

From the chain theory of inhibition of oxidation processes it is seen that inhibitors
should be introduced at an earlier stage of the technological process of fat production, when
free radicals in the system are not many. Some antioxidants are capable of inhibiting the
process at sufficiently advanced stages of oxidation, but they are quickly consumed, so their
action is short.
By the example of inhibiting pork fat at the stage of rather well advanced oxidation,
the possibility of inhibiting the oxidation reaction was shown, but if the antioxidant were
introduced into fat at an earlier stage of oxidation, its efficiency would have been several
times larger. This is illustrated by the kinetic curves of Fig. 1.9.
The chain reaction of oxidation could be inhibited not only by increasing the breakdown of chains, as it takes places in the case of phenolic and some other antioxidants
(quinones, amines), but also by decreasing the rate of free radical formation by the degenerate branching reaction. Introduction of substances (e.g., some thio compounds), which interact with hydroperoxides without forming free radicals, into the oxidizing system also
makes it possible to reduce the oxidation reaction rate.
Sulfurous compounds are much less active in inhibiting the oxidation processes than,
e.g., antioxidants of the type of alkylphenols, even if they are introduced in considerable
amounts. However, being added into the oxidizing system together with an antioxidant of
phenolic nature, they enhance the efficiency of its action significantly. Herewith, the length
of the induction period proves larger than the sum of the induction periods stipulated by
each substance separately.
This non-additive antioxidative action of a combined addition of two (or more) substances was called synergism.
In processes of inhibited oxidation, synergists are commonly substances, which by
themselves either possess no antioxidative action at all, or are weak antioxidants but enhance the efficiency of action of other inhibitors.

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Peroxide numbers, % iodine

48

0.16

1
4

0.12

0.08
0.04

6
Time, h

10

12

Figure 1.9 Kinetic curves of oxidation of pork fat at 100C in the presence of 0.01% butyloxyanisol
introduced into fat at various stages of oxidation: 1, initial, oxidized up to the peroxide number; 2,
0.008; 3, 0.026; 4, 0.045.

Synergists include thio compounds, phosphatides, some organic and inorganic acids,
amino acids, polyphosphates etc.
The listed groups of substances are so diverse from the chemical point of view that one
can not assume the existence of a synergic-action mechanism common for them.
One thing is considered to be undoubted, though, that in the case of a synergism each
of two components is involved in the oxidation inhibition process in a different way.
For some synergists, a credible view of the mechanism of their action is as of hydrogen
donors, which leads to the restoration of the initial form of the antioxidants. For instance,
the reversible conversion of quinones to hydroquinones creates a possibility, when the same
molecule of the inhibitor breaks several chains. This mechanism of the process is what explains a sharp increase of the efficiency of action of the inhibitor.
The synergic action of some amino acids is stipulated by their ability to reduce oxidized phenolic antioxidants.
Ascorbic acid and its fatty-acid ethers are readily oxidized and reduced
OH OH
C

2H
+2H

Due to their ability to donate hydrogen atoms, these compounds can regenerate oxidized phenolic antioxidants. Simultaneously, ascorbic acid is a metal deactivator, forming
neutral monometal salts at the expense of one of the enol atoms of hydrogen.
Metal deactivators are substances, which inhibit the catalytic activity of metals. Deactivators are used in the cases when the oxidizing system in the process of oxidation is in
contact with the metal surface and, corroding it, forms salt catalysts from variable-valence
metals.
A strong metal deactivator is citric acid, which forms complex compounds with metal
ions. These compounds are capable of binding iron traces occurring in fats and take them
out of the reaction. Polyoxycompounds sorbitol, sugars and their derivatives also possess an ability to bind metals.

CHAPTER 1

49

Owing to the synergism between oxidation inhibitors, there is a possibility of increasing the antioxidative efficiency of a number of substances and, besides, decreasing their
concentration in the oxidizing system. The use of additives, which deactivate traces of
variable-valence metals in many cases getting into a product in the process of production,
enhances the inhibition of the oxidation process even more.
Thus, studies of the mechanism and chemistry of the oxidation processes and their inhibition enabled practical applications of particular antioxidants and efficient antioxidative
compositions for increasing the storage times of fats, and in some cases, of fat-containing
products.
1.4.8 Characteristics and application of antioxidants and synergists
At present, a large amount of substances possessing the properties of oxidation inhibitors
are used in practice.
Storage times of edible fats and technical fats, as well as fat-containing food products
are extended using individual antioxidants, mixtures of antioxidants, as well as compositions of one or several antioxidants with various synergists and metal deactivators.
A commercial product butyloxyanisol (BOA) consists of a mixture of two isomers:
2- and 3-tert-butyl-4-oxyanisols (3- and 2-tert-butyl-4-methoxyphenols).
OCH3 CH
3
C

OCH3
CH3

CH3

CH3
OH

2-tert-butyl-4-oxyanisol

OH

CH3

CH3

3-tert-butyl-4-oxyaniso

The ratio of the isomers depends on the manufacturing method of BOA. The 3-isomer
possesses a slightly larger antioxidative efficiency than the 2-isomer. Both isomers exhibit
some synergism, so that the mixtures containing a large amount of isomer are close to pure
3-tert-butyl-4-oxyanisol by their efficiency. In commercial mixtures, the content of 3-isomer is no less than 85%. The antioxidative efficiency of butyloxyanisol increases up to a
concentration of 0.02% in the substrate.
Butyloxyanisol is represented by waxlike crystals of cream or rose-cream colour,
which possess a phenolic smell. The melting temperature of the mixture of isomers is
4855C. Each isomer melts at a temperature of about 65C.
Butyloxyanisol does not change the colour of food products and at small concentrations has no effect on their taste and flavour. It is rather stable to the action of high temperatures and can be added into products subjected to searing, boiling and baking. It is also
capable of inhibiting oxidation of not only pure fats, but also fats added into products. The
solubility of butyloxyanisol at 25C is as follows (in percent): in water, 0; ethyl alcohol, 25;
pork rendered fat, 50; propylene glycol, 50; cotton oil, 30; peanut oil, 40.
At a concentration of 0.010.02%, butyloxyanisol was proved by several investigators
to protect pork rendered fat from oxidation well (Fig. 1.10).
Butyloxyanisol is widely used alone or in combination with other antioxidants
nordihydroguaiaretic acid, propyl gallate, butyloxytolyene, tocopherol to inhibit oxidative processes in animal fats and fat-containing products. The efficiency of action of the

50

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

0.20

Peroxide numbers, % iodine

1
0.16

0.12

0.08

0.04

0
0

Figure 1.10
oxyanisol.

4
6
Time, h

Kinetic curves of oxidation of pork fat at 100C: 1, no antioxidant; 2, with 0.01% butyl-

antioxidant is enhanced by adding such synergists as citric acid, triethylphosphate,


methionine, lecitin and thiodipropionic acid.
An idea of the synergistic effect of a mixture of butyloxyanisol and thiodipropionic
acid added to lard can be given by the data presented below.
Inhibitor
No additives
0.01% butyloxyanisol
0.01% thiodipropionic acid
0.01% butyloxyanisol + 0.01% thiodipropionic acid

Induction period, h
2
38
19
81

Butyloxyanisol in combination with other antioxidants and synergists inhibits rancidification of fats in pork, turkey, in various fish-liver oils, and in diverse vegetable oils, in
fried potatoes, and in dough items.
Pork rendered fat used for frying some chips, alone or in combination with vegetable
oils, should be subjected to obligatory antioxidant treatment. Usually, a composition of butyloxyanisol, propyl gallate and citric acid is used, which is introduced either into the frying
fat, or into salt, or partially into the fat and salt. Approximately 0.1% of the antioxidant composition is added.
Butyloxyanisol proved an efficient antioxidant of packaging materials intended for
storage of fat-containing products, dehydrated soups, as well as frozen pork. A mixture consisting of butyloxyanisol, nordihydroguaiaretic acid and ascorbic acid increases the stability
of chopped pork and turkey.
Addition of 0.003% butyloxyanisol and 0.001% citric acid to dry-cured sausages is
permitted in the USA.
Investigation of the toxicity of butyloxyanisol enables assigning it to the group of

Peroxide numbers, % iodine

CHAPTER 1

0.20

0.16

51

0.12
0.08
0.04
0
0

10 12 14 16 18 20
Time, h

Figure 1.11 Kinetic curves of accumulation of fat peroxides in oxidation of beef fat: 1, no antioxidant; 2, in the presence of an antioxidant mixture (0.01% BOT + 0.005% PG + 0.005% citric acid).
Oxidation temperature, 122C.

low-toxic food supplements. The acute-toxicity test of this inhibitor showed its LD50 for
rats to be within 29005000 mg/kg weight and for mice 12502000 mg/kg weight.
A prolonged feeding of animals the food containing a moderate amount of butyloxyanisol did not lead to any deviations in their organism.
The dose causing no significant toxic effect in rats is 0.5% BOA in food, which is
equivalent to 250 mg/kg body weight per day.
Butyloxytolyene (2,6-di-tert-butyl-p-cresol; 2,6-di-tert-butyl-4-methylphenol) is a
screened phenol. Depending on its purity and manufacturer, it is known under the names of
BHT (BOT), Ionol CP (ionol), antioxidant AC-1, AC-3, topanols OC, A, O etc.
CH3
CH3

CH3

CH3

CH3

OH

CH3

CH3

2,6-di-tert-butyl-p-cresol
Butyloxytolyene is represented by colourless crystals without taste and smell with the
melting temperature of 70C. Butyloxytolyene is not soluble in water and propylene glycol,
but is well soluble in fats. At 25C, 40% of the antioxidant dissolves in pork rendered fat
and beef fat. The presence of iron traces does not change the colour of products.
The crude preparation has a yellow colour and characteristic smell. It is purified by
vacuum distillation followed by recrystallization from ethanol or only recrystallization, depending on the impurity of the antioxidant.
In the UV region of the spectrum, butyloxytolyene has two absorption maxima at
wavelengths of 284 and 277 m.
Butyloxytolyene alone or in a mixture with other antioxidants and synergists (butyloxyanisol, propyl gallate, citric acid) increases the resistance to oxidation of beef fat, pork
fat, milk fat and butter, cotton oil and shortenings.
An antioxidative mixture consisting of butyloxytolyene, propyl gallate and citric acid
increases the resistance to oxidation of beef fat ninefold (Fig. 1.11), as well as protects
against oxidation carotene contained in fat. A pronounced synergic effect is observed at the
combined presence of butyloxyanisol and butyloxytolyene in lard.

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Peroxide numbers, % iodine

52

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0

3
0

4
Time, h

Figure 1.12 Kinetic curves of accumulation of peroxides in oxidation of a mixture of ethyl esters of
linolic and linolenic acids: 1, control; 2, with 0.02% BOT; 3, with 0.3% BOT. Oxidation temperature,
60C.

The antioxidative properties of BOT are carried over to products, e.g., biscuits containing fats produced with this antioxidant; however, this effect is smaller than with BOA.
The efficiency of action of BOT increases with the increase of its concentration in the
substrate.
Butyloxytolyene inhibits the development of oxidation not only in edible fats but also
in most diverse systems subject to oxidation: resins, technical fats, waxes, oils, plastics etc.
At large concentrations, butyloxytolyene inhibits oxidation even in such readily oxidizing systems as mixtures of linolic and linolenic acid esters (Fig. 1.12). It is also used as
an antioxidant of packaging materials intended for storage of fat-containing products.
Butyloxytolyene homologues 2,6-di-tert-hexyl-, 2,6-di-tert-heptyl- and 2,6-di-tertoctyl-4-methylphenols are no less efficient, and 2,6-di-tert-amyl-4-methylphenol is more
efficient as an antioxidant of pork rendered fat than 2,6-di-tert-butyl-4-methylphenol.
Acute toxicity studies of BOT on rats showed its LD50 to be within the limits of
17002450 mg/kg weight; for mice this value was 2000 mg/kg body weight. The content
of up to 0.8% BOT in rat ration does not lead to significant pathological changes provided
the content of fat in the feed is less than 5%. Addition of 10 or 20% lard to the food enhanced
the harmful effect of BOT.
As the result of long-time toxic studies of this antioxidant on animals, it was concluded
that it can be used as a food supplement, though it is considered to be necessary to continue
studies, in particular, on the effect of BOT on lipid metabolism.
Gallic acid (3,4,5-trioxybenzoic acid) is a constituent part of tannin and is contained
in tea and pomegranate juice:
OH
HO

OH
COOH

Gallic acid
Gallic acid is a white powderlike substance, which darkens in the light. It melts at a
temperature of 235C (to decomposition). It dissolves in water, ethyl alcohol and is poorly
soluble in fats. In the presence of iron, it stains blue-black.

CHAPTER 1

53

Gallic acid is a very strong phenolic antioxidant capable of acting synergistically with
other antioxidants. Its antioxidant efficiency in stabilization of carotene of animal fats and
vegetable oils proved to be high. In spite of this, its addition into edible fats is not permitted.
Possibly, this is due to the fact that, being well soluble in water, it dissolves in fats very
poorly. Esterification of the carboxyl group of gallic acid by normal aliphatic alcohols
makes it possible to improve its solubility in fats and to decrease its solubility in water.
Lower esters of gallic acid are poorly soluble in water and fats, higher esters are in fact insoluble in water but are comparatively well soluble in fats.
Propyl gallate PG (normal propyl ester of gallic acid):
OH
HO

OH
CO

OC3H7

Propyl gallate
Propyl gallate is a light-cream fine crystalline powder without smell with a light bitter
taste. Its melting temperature is 146148C. In concentrations applied, it does not affect
the organoleptic properties of fat. In the presence of iron traces, this antioxidant stains the
product. The emergence of a blue-black coloration it can be eliminated or weakened by citric acid or another metal deactivator. Propyl gallate dissolves in ethyl alcohol, propylene
glycol, glycerol and is rather poorly soluble in fats and oils. It inhibits efficiently the oxidation of pork rendered fat, milk fat, herring oil, cotton oil. It is also successfully used in a
mixture with other antioxidants and synergists (BOA, citric acid). Propyl gallate lends a
high resistance to oxidation to neutral and slightly acidic fats and fatty products, not subject
to the action of high temperatures. It is unstable to heating and the action of weak alkali.
The decomposition rate of propyl gallate in lard was studied under conditions of broiling. The data of this study are given in Table 1.6.
Table 1.6
Heating time, h

0
1
2
8
16

Content of propyl gallate in lard, %, at temperature, C


162

190

0.0058
0.0052
0.0050
0.0032
0.0002

0.0058
0.0048
0.0037
0.0008
0.0000

The antioxidative activity of gallic acid ethers (isoamyl gallate, nonyl gallate, butyl
gallate, methyl gallate, propyl gallate) in pork fat are characterized by the data presented in
Fig. 1.13. Addition of 0.01% of each gallate increased the resistance of fat to oxidation
68-fold.
Octyl and dodecyl gallates (esters of gallic acid with n-higher fatty alcohols octyl
and dodecyl alcohols):

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Peroxide numbers, % iodine

54

0.20

0.15

0.10
0.05
0
0

11

13

Time, h

Figure 1.13 Kinetic curves of accumulation of peroxides in oxidation of pork fat with additives of
different gallates: 1, control; 2, isoamyl gallate; 3, nonyl gallate; 4, butyl gallate; 5, methyl gallate; 6,
propyl gallate. Oxidation temperature, 110C.

OH
HO

OH
OH

CO

Propyl gallate

HO
C6H17

OH
CO

C12H25

Dodecyl gallate

By their appearance, both antioxidants are crystalline substances of light-cream colour


without smell, with a weakly bitter taste. They have no effect on the organoleptic properties
of fat. The melting temperature of octyl gallate is 9495C; of dodecyl gallate, 96.597C.
These esters are almost insoluble in water, well soluble in glycerol, ethyl alcohol and
satisfactorily soluble in fat.
Octyl and dodecyl gallates in the presence of iron and its salts change the coloration
of food products. To eliminate the coloration, it is recommended to use metal deactivators.
Higher gallates are widely used for protection of fats and fat-containing products from
oxidation. They also inhibit the oxidation of fat-soluble vitamins and carotene.
Higher gallates are added to edible fats in various amounts depending on the purpose
of the product. Addition of 0.005% octyl gallate to lard increases its storage time up to approximately one year; and of 0.01%, up to two years.
Higher gallates inhibit well the oxidative processes in pure fat, as well as in fats present
in food products. They are efficient for protection from oxidation of dry dairy products.
The data on the toxicological studies of propyl, octyl and dodecyl gallates are consolidated in materials of the World Health Organization. According to these data, acute toxicity of these compounds in peroral introduction to animals is as follows:

Antioxidants
Propyl gallate
Propyl gallate
Octyl gallate
Dodecyl gallate

Animals

LD50 (mg/kg weight)

Mice
Rats
Mice/rats
Mice/rats

20003500
36003800
4700
6500

CHAPTER 1

55

According to other data, LD50 for propyl gallate is 1700 mg/kg weight for mice and
2600 mg/kg weight for rats. However, chronic experiments have found a slight adverse effect of this compound. A retardation of growth and lower resistance to partial starvation was
observed in rats given fat with propyl gallate in their diet.
No essential differences were found between control and test groups of three generations of rats given a diet containing 7% of fat and 0.2% of octyl and dodecyl gallates.
Experiments on long-time feeding (over the space of 13 months) white rats a higher
dose of dodecyl gallate (0.4% in the ration) did not lead to a change in the behaviour and
appearance of rats; no difference in weight was observed, either.
The data of a morphological study of the blood as well as the hemoglobin content in
the blood varied in rats of the test and control groups within the same limits. No effect of
dodecyl gallate on the redox enzymes of the blood was found; there were no changes in the
organs of test-group animals.
Based on the studies conducted, no harmful effect of fat with dodecyl gallate on test
animals was revealed.
The dodecyl gallate concentration of 0.01% (twenty times smaller than in the test animals) in edible fats can be considered permissible.
Nordihydroguaiaretic acid (NDGA) is contained in considerable amounts in leaves
and stems of the plant Larrea divaricata:
OH
HO

OH

CH3 CH3
CH2

CH

CH

CH2

OH

NDGA
NDGA 4,4(2,3-dimethyl tetramethylene)-dipyrocatechin.
NDGA is a white or yellow-gray crystalline powder with the melting temperature of
184185C. At a concentration of up to 0.1%, it does not change the colour, taste and smell
of pork rendered fat.
NDGA is weakly soluble in water and diluted acids. Its solubility in fats is about 0.5%,
but upon heating up to 125150C it reaches approximately 5%. In cooling, a major part
of NDGA is precipitated, but about 1% remains in fat in a dissolved form or in the form of
thin suspension. It can also be introduced into fat in ethyl alcohol or acetic acid followed
by their removal by heating under vacuum.
NDGA imparts high stability to oxidation to neutral and weakly acidic products, does
not form coloration in the presence of iron. In some cases, it lends a product a slightly bitterish taste in long-time storage. NDGA is unstable to the action of high temperatures (in
broiling) and weak alkali.
A number of works note a high antioxidative efficiency of NDGA in stabilization of
lard, beef fat, bacon, carotene, vitamin A, cow butter.
NDGA is used together with synergists (ascorbyl palmitate; phosphoric, ascorbic and
citric acids) to increase the stability of lard, bacon and other products. Introduction of
thousandth fractions of a percent of NDGA to the fat part of bacon ensures a significant
antioxidative effect.
Only to a very minor extent, the antioxidative efficiency of NDGA is transferred to the
product into which NDGA-containing fat is added. It inhibits very well the oxidation in
waterfat systems, especially in the presence of synergists. In this case, it inhibits the

56

Peroxide numbers, % iodine

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

0.15
1
0.10
2

0.05

12

16

20
24
Time, h

28

32

36

40

Figure 1.14 Kinetic curves of oxidation of pork fat at 90C): 1, no antioxidant; 2, with 1% tocopherol; 3, with 0.1% tocopherol.

development of oxidative spoilage catalyzed by meat and blood pigments and their
derivatives.
The toxicological study of NDGA has shown that LD50 for mice is within the limits
of 20004000; for rats, 20005000; for guinea pigs, 830 mg/kg body weight.
Chronic experiments carried out in limited quantities have not led to more or less unequivocal results, which does not make it possible to give a toxicological evaluation for
NDGA and at the same time to set a permissible daily dose for man.
Tocopherols (vitamin E). By their chemical structure, they are derivatives of 6-oxychroman.
CH3

CH8

HO

CH3

CH2(CH2CH2CHCH2)2CH2CH2CHCH3
CH3

CH3

CH3

-Tocopherol (5,7,8-trimethyl tocol)


Tocopherols are widespread in nature.
Besides -tocopherol, other tocopherols have been isolated from natural sources:
-tocopherol (5,8-dimethyl tocol), -tocopherol (7,8-dimethyl tocol), -tocopherol
(8-methyl tocol) etc.
Vitamin E is a rather stable compound. It is stable to the action of high temperatures,
prolonged boiling in water, but is decomposed by UV light and some oxidants.
Vitamin E is soluble in oils and fat solvents.
Tocopherols are natural antioxidants of fats, apparently, preventing the formation of
peroxides in the living organism.
Fats isolated from the animal organism or from plants is the stronger to rancidification,
the more tocopherols they contain.
Animal fats contain 0.23 mg% of tocopherols; in vegetable fats, they are 90280
mg%, i.e., the almost optimal concentrations. Therefore, tocopherols stabilize animal fats
well and are inefficient for vegetable oils.

CHAPTER 1

57

The antioxidative efficiency of tocopherols is higher at low concentrations. Their introduction into fats at too high concentrations not only fails to enhance the antioxidative
effect, but in some cases leads to an adverse change of organoleptic parameters.
The increase of the stability of pork rendered fat, into which a 0.1% concentrate of vitamin E obtained by the method of molecular distillation from soybean oil was added, is
indicated by the data presented in Fig. 1.14.
Tocopherol isomers are not equivalent by their antioxidative efficiency, and it is not
proportional to their vitamin activity. For pork fat, the most efficient antioxidant is -tocopherol, but -tocopherol is also successfully used for this purpose.
Feeding animals with tocopherols also increases the stability of fat and fatty meat to
oxidation. However, only a minor part of tocopherol is preserved in fat.
Tocopherols were found to stabilize fats present in baked and fried products.
A large number of works deal with stabilization of fats by various compositions of
plant origin, which contain vitamin E (extracts of vitamins from wheat, a petroleum-ether
extract from maize grains, oil of wheat and maize seedlings).
Soybean flour, maize and barley flour, rice bran, rye and pea flour, flour from cotton
seeds, cocoa seeds, oats flour possess antioxidative properties.
Oats have been found recently to contain aliphatic alcohol-esterified 3,4-dioxycinnamoyl (caffeoyl), which possesses an antioxidative activity. The following esters were
isolated: 1-caffeoyl glycerol, 1-palmitoyl 2,3-dicaffeoyl glycerol and 1,2,3-tricaffeoyl glycerol. Their antioxidative activity in oats oil is similar to the activity of propyl gallate and
BOT.
Besides these antioxidants, many other substances and groups of substances have been
proposed, which possess antioxidative properties.
Eugenol and its derivatives possess good antioxidative properties with respect to soybean oil and citrus ether oils. The raw material for eugenol is ether oil of colluria and basil
oil. Sesamol attributed to the group of phenols (3,4-methylene dioxypenol) was obtained
from the unsaponifiable shelf fungus of gingili oil. By the efficiency of action in lard, it is
not inferior to nordihydroguaiaretic acid.
The antioxidative properties of 2,4,5-trioxyphenons have been studied. Antioxidants
of this type were proposed for fats, carotene and other products, as well as for preparing
feeds with fat for poultry and cattle. Ethoxyquine (2,2,4-trimethyl-6-ethoxy-1,2-dihydroquinolin) was proposed as a better feed antioxidant for protection of carotene of dried alfalfa
and carotene and vitamin A in mixed feeds. In the USA, it is permitted to be added into
poultry feed. Butyloxytolyene can also be used for inhibition of oxidation of animal fats
added into feeds, or to be added into feeds in a finely ground form.
Conidendrin is an antioxidant belonging to the group of polyphenols; it occurs in resinous trees. By its antioxidative efficiency for lard, it is close to nordihydroguaiaretic acid.
Guaiacum resin has been used for many years in some countries (USA, Austria, Canada
etc.). It also inhibits the oxidation of fats in dehydrated pork and frozen meat.
The antioxidative efficiency of tannins has been confirmed by patent applications and
research work. Many natural spices possess antioxidative properties; they slow down rancidification of fats, including in chopped frozen pork and beef.
The antioxidative properties of many kinds of spices (cloves, rosemary, sage, ginger,
black pepper etc.) have been found. The lipid fractions of tomatoes and carrots possess antioxidative properties.
The antioxidative properties of some substances belonging to the group of flavonoids
(quercitin, dihydroquercitin, pomiferin, catechin) have been studied. Upon addition of 0.1%

58

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

1.000

TBA numbers

0.900
0.800
1

0.700
0.600

2
0.500

3
4

0.400
0.300
10

20

30
40
50
Time, days

60

70

80

Figure 1.15 Dependence of the amount of oxidation products reacting with TBA on storage time of
sausages stabilized by (concentration of antioxidants, 0.02%): 1, control; 2, butyloxyanisol; 3, ascorbic acid; 4, sodium gentisate; 5, gentisic acid.

each of quercitin and propyl gallate to fats, the antioxidative effect was the same. Quercitin
inhibits the oxidation of pork fat in the presence of copper(II) no less satisfactorily than butyloxytoluene, owing to the ability of flavonoids to form complexes with heavy metals.
Crystalline amino hexose reductons obtained from hexoses and secondary amines
were found to have a high antioxidative activity in various animal fats.
Smoking fluids were found to possess rather strong antioxidative properties due to the
content of phenols in them.
In the recent years, gentisic acid (2,5-dioxybenzoic acid) and its sodium salt were
again proposed as antioxidants of lard and other edible fats. The efficiency of these substances in the inhibition of oxidation of lard is the same as that of butyloxyanisol. They inhibit the oxidative processes in unsalted frozen bacon and sausages. The comparative
evaluation of gentisic acid, sodium gentisate, ascorbic acid and butyloxyanisol are presented in Fig. 1.15.
Esters of sorbic acid propyl, allyl, butyl, isoamyl, hexyl, nonyl and decyl were proposed as substances inhibiting the oxidation of hydrogenated whale blubber. It is seen in
Fig. 1.16 that each of the esters studied possesses an ability to increase the stability of hydrogenated whale blubber in storage. There are yet no data as to whether these compounds
can be considered as antioxidants or should be attributed to synergists.
Frequently, additives possessing the properties of synergists are introduced into antioxidative compositions. Many of them are metal deactivators.
Some acids and their derivatives. Citric acid. Many works note the positive effect
of citric acid on the stability of fats and oils in storage. Citric acid forms soluble complex
compounds with metal ions. Application of this acid is made difficult by the fact that it is
not soluble in fats and is to be introduced into fats in propylene glycol or ethyl alcohol.
Therefore, frequently fat-soluble esters of citric acid are used, e.g., isopropyl citrate, stearyl
citrate. These esters are used independently or with phenolic antioxidants. Besides citric

CHAPTER 1

59

0.10
1

Peroxide numbers, % iodine

0.08

0.06

0.04
2
5
0.02

6
8
3
4
7

0
5

10
15
Time, days

25

Figure 1.16 Change of the peroxide numbers in hydrogenated whale blubber during its storage at
room temperature: 1, control; upon addition of: 2, 0.02% propyl ester of sorbic acid; 3, 0.02% allyl
ester; 4, 0.02% butyl ester; 5, 0.02% isoamyl ester; 6, 0.02% hexyl ester; 7, 0.02% nonyl ester; 8,
0.02% decyl ester.

acid, it is recommended to use oxalic, malonic, maleic, fumaric and other organic acids, as
well as mineral acids phosphoric and sulfuric.
Ascorbic acid and its derivatives Ascorbic acid (vitamin C) is a crystalline compound readily soluble in water.
Ascorbic acid and its dehydro derivative form a redox system, which can donate and
accept hydrogen atoms.
In the recent years, ascorbic acid and its stereoisomer D-iso-ascorbic acid became
widespread in food industry as synergist antioxidants:

HO

HO

HO

CH2OH

Ascorbic acid

HO

HO

OH

CH2OH

D-iso-ascorbic acid

60

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Ascorbic acid is an oxidation inhibitor for lard and other fats. Together with -tocopherol, it has a very strong inhibitory effect. Besides, ascorbic acid can retard oxidative
changes of muscle tissue and blood pigments. There are indications that sometimes ascorbic
acid contributes to oxidation, e.g., when it is in contact with animal fat, in which the content
of tocopherol is insignificant.
Contrary to true antioxidants, which inhibit oxidation processes even at advanced
stages, ascorbic acid in similar cases not only fails to inhibit the development of oxidation
but even accelerates it. By the example of animal fats, it was shown that addition of ascorbic
acid at the stage of oxidation, when the peroxide number was higher than 0.05 (% iodine),
has a catalytic action. Ascorbic acid is recommended to be used for stabilization of those
fats, which contain natural or added antioxidants. Owing to its solubility in water, ascorbic
acid is used for inhibition of oxidative processes in emulsions of fats and oils, and its sodium
salt
O

HO

NaO

HO

CH2

OH

for inhibition of oxidation in packaged meat.


In introduction of both substances with food, LD50 for rats, mice and other animals
was found to be >5000 mg/kg body weight.
D-iso-ascorbic acid (3-keto-D-glucofuranolactone, erythorbic acid), which possesses
no vitamin C activity, found use as an oxidation inhibitor in emulsions of fats and oils, as
well as meat and meat products.
The sodium salt of erythorbic acid is used for treatment of fatback before smoking. It
retards oxidation and contributes to the development and fixation of a reddish tint.
A 1% content of erythorbic acid in food, which is equivalent to 500 mg/kg body weight
(rats) does not lead to any significant toxic effect.
Esters of ascorbic acid with high-molecular-mass fatty acids. Of special interest are
fat-soluble derivatives of ascorbic acid: esters with aliphatic acids palmitic, stearic, myristinic, and others.
Esters of ascorbic acid do not impart fats with undesirable smell, taste and colour.
Ascorbyl palmitate is a white or yellow-white powder with a smell similar to that of citrus
fruits. The melting temperature of ascorbyl palmitate is 112113C:
OH OH
O

OH
CH

CH

CH2

CO(CH2)14

CH3.

Ascorbyl palmitate and other synthetic esters increase the stability of fats and oils to
oxidation. They are very efficient in vegetable oils; their synergist action manifests itself
well with phospholipids and -tocopherol.
The antioxidant efficiency of ascorbyl palmitate in pork fat containing natural inhibi-

CHAPTER 1

61

tors is close to the efficiency of butyloxyanisol. The combined application of ascorbyl


palmitate and butyloxyanisol is especially efficient.
The presence of ascorbyl palmitate in butyloxyanisol-stabilized beef fat retards the appearance of a greenish tint in it during refrigerator storage.
There have been no reports of acute toxicity of ascorbyl palmitate in the literature. A
0.25% content of this substance in daily diet, equivalent to 125 mg/kg body weight, has no
noticeable toxic effect on rats.
Many amino acids possess an ability to retard the oxidative spoilage of edible fats. Histidin and arginin inhibit well the oxidation of edible fat. They exhibit a significant synergism with phenolic antioxidants -tocopherol, nordihydroguaiaretic acid and gallic acid
ethers.
Phosphatides are widespread in nature. In the literature, there are often contradictory
data on phosphatides as inhibitors of oxidation of fats and oils. This is, apparently, due to
the fact that phosphatides are a complex mixture of plant or animal phospholipids. Besides,
they include unsaturated fatty acids, which are readily oxidized when they get phosphatides.
Lecithin was one of the first antioxidants of edible fats to be used.
There are indications that phosphatides alone in the absence of phenolic-type antioxidants weakly increase the stability of lard.
Some works indicate that a minor addition of commercial soy lecithin succeeded in
retarding the oxidation of lard, cotton oil and other fats, as well as vitamin A.
However, cases are known when storage of products with a lecithin addition led to
their darkening and unpleasant smell.
The lecithin and kephalin fractions of soybean, sunflower and flax phosphatides have
almost the same efficiency in stabilization of sunflower oil.
Kolamin a constituent part of kephalin has an inhibitory action on the oxidation of
some fats. There are recommendations on the application of ascorbic acid together with
kolamin for stabilizing fats and preserving vitamin A in them.
Mixtures of carbohydrates and phosphatides for stabilization of lard, bacon and other
products have been patented.
Addition of lecithin does not prevent uncooked smoked sausages from oxidative spoilage and deteriorates their taste. The synergic action of phosphatides is dealt with in a large
number of works.
It has been found that thiodipropionic and thiodiacetic acids are capable of inhibiting
oxidation.
S

CH2

CH2

COOH

CH2

CH2

COOH

Thiodipropionic acid
Thiodipropionic acid was proposed as a stabilizer of oxidation of fats and oils. This
acid in combination with butyloxyanisol exhibits a significant synergism. Its LD50 in
studies on mice was found to be 2000; in rats, it was 3000 mg/kg body weight (perorally).
For such derivatives of thiodipropionic acid as dilauryl thiodipropionate and distearyl thiodipropionate, which are also used as inhibitors of oxidation of fats and food products, LD50
for mice was >2000 mg/kg; and for rats, >2500 mg/kg body weight. A 3% content of these
substances in the diet, which is equivalent to 1500 mg/kg body weight per day, has no
noticeable toxic effect.
In a number of countries, thiodipropionic acid is permitted for addition to edible fats.

62

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Nevertheless, it has not found widespread use, as mercaptans or other sulfur-containing


products with an unpleasant smell can form during its decomposition.
Tetraalkyl tiuram disulfides are recommended as substances inhibiting the oxidation
processes in edible fats. This group of compounds includes tetraethyl tiuram disulfide
(TETD) or antabus:
CH3

CH2

CH3

CH2

C
S

CH2

CH3

CH2

CH3

The application of these preparations for increasing the stability of fats and oils has
been patented.
Besides, such sulfo compounds as thiourea, thiouracyl, cystin were studied as stabilizers of fats, fatback and other fat-containing products together with a rice-bran concentrate.
Phosphates. The salts of phosphoric acid have long been proposed to be used to increase the stability of fats and fat-containing products to oxidation.
Polyphosphates belong to a very small number of oxidation inhibitors, which exhibit
their action in the presence of water. They inhibit oxidation even in the presence of heme
pigments.
Table 1.7 presents a comparative assessment of the antioxidative efficiency of various
polyphosphates added into chopped pork meat. For the assessment, the reaction with
2-thiobarbituric acid (TBA) was used; the results are expressed in units of optical density
at a wavelength of 538 m.
Table 1.7
Added phosphate (0.5% of the weight of a meat
product)

No additives, control
Sodium tripolyphosphate
Sodium hexametapolyphosphate
Sodium tetrapyrophosphate
Orthophosphate

Optical density
before storage

one-week storage at
4.4C

1.200
0.192
0.168
0.176
1.200

5.500
0.334
0.270
0.255
5.450

Tripolyphosphate, hexametaphosphate and tetrapyrophosphate are efficient additives


for pork. Their efficiency increases at the addition of ascorbic acid.
Polyposphates in combination with ascorbic acid were found to play a positive role in
inhibition of oxidation in boiled meat.
Studies of the antioxidative action of polyphosphates on meat products subjected to
brining have found that polyphosphates contribute to the preservation of their coloration
and retard the oxidation of fat.
For inhibiting the oxidative spoilage of fat in bacon and sausage products, it is recommended to add polyphosphates into cover brines and syringe brines.
A significant antioxidant efficiency of action of a mixture of tripolyphosphate with sodium ascorbinate on roasted beef slices was established. Beef slices were immersed into a
solution containing 1% tripolyphosphate (Na5P3O10) and 0.27% sodium ascorbinate. The
effect of this treatment on the change of oxidation products reacting with 2-thiobarbituric

63

CHAPTER 1

acid (TBA) and the organoleptic parameters of the roasted beef slices during their storage
in a refrigerator and in a freezing chamber is seen from the data presented in Table 1.8.
Treatment of poultry carcasses with solutions of phosphates provides for the inhibition
of the oxidative processes in fat. Phosphates also decrease the losses of meat fluid in the
culinary treatment of the carcass. Depending on the size, the carcass is immersed into a 6%
phosphate solution for 624 h or into a 15% solution for 1.24 h.
Binding of traces of variable-valence metals is ever more recommended to be done by
using some salts of ethylene diamine tetraacetic acid (EDTA). The use of these compounds
in combination with antioxidants considerably increases the stability of lard and other food
products to oxidation.
Table 1.8
Storage
temperature,
C
1

26

Storage time,
days
1
4
7
11
18
11
31
45
81
164

Controls

Tested samples

TBA number smell, score** TBA number


11.5
15.2
19.5
21.1
21.2
3.5
2.3
3.2
4.9
4.1

2.5
2.6
1.9

2.7
2.4

2.2
3.5

0.3
0.4
0.3
0.3
0.3
0.2
0.2
0.2
0.2
0.2

smell, score*

5.6
5.3
4.7

5.4
5.5

5.9
5.8

* *Score 6 indicates the absence of smell, score 1, a strong rancid odour.

1.4.9 Comparative efficiency, methods of treatment and admissible concentrations


of antioxidants
A number of original works give a comparative evaluation of many antioxidants, synergists
and metal deactivators as applied to various fats and model systems, a major part of which
is dealt with in monographs. As as example, Fig. 1.17 compares the efficiencies of several
inhibitors of oxidation of pork rendered fat. As this kind of fat contains little natural inhibitors tocopherols addition of one synergist is the least efficient.
The most suitable inhibitors of animal rendered fats are phenolic antioxidants, preferably with addition of a synergist.
The choice of an antioxidant or an antioxidant mixture becomes much more complicated if fat is a component of a food product, because in this case it is in contact with moisture and various food components. If there is water in the system, the antioxidant should be
relatively soluble in fat and water. Water-insoluble inhibitors are more suitable for dry
fat-containing products.
When using antioxidants, a matter of importance is the moment of their introduction
into fat, so that to inhibit the development of the chain reaction of oxidation as soon as possible. Antioxidants can be introduced into raw materials before rendering, before settling
or draining off the fat into barrels. Below, we present the results of model experiments.

64

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Peroxide numbers, % iodine

0.20

0.16

0.12

0.08

0.04

12
Time, h

16

20

24

Figure 1.17 Kinetic curves of accumulation of peroxides at a temperature of 110C during the oxidation of pork pat in the presence of 0.01% antioxidant: 1, no antioxidant; 2, ascorbyl palmitate; 3,
dodecyl gallate; 4, octyl gallate; 5, butyloxytolyene; 6, butyloxyanisol; 7, propyl gallate.

Point of introduction of 0.01% BOA

Induction period, h

Before rendering
Before settling

10.0
11.8

After settling

10.5

As seen, the greatest effect is achieved at the introduction of BOA into fat before settling and the lowest effect before rendering, which can be explained by adsorption of the
antioxidant by proteins of connective tissue.
Therefore in rendering fat in kettles the antioxidant should be introduced before settling.
For fats produced in automatic fat-rendering units (e.g., Titan), antioxidants can be introduced only at one point of the technological process before draining off into barrels.
Pork fat or another animal fat is accumulated in the receiver. After filling the receiver,
the supply of fat to it is stopped. Fat (35 kg, temperature usually 80C) is poured from the
receiver into a small vessel, into which the antioxidant or antioxidative mixture is added;
the contents are mixed to dissolution, poured back into the receiver and mixed with the
entire bulk for 10 min, after which fat is drained off into barrels.
The surface treatment of slabs of meat and other products is performed by sprinkling
with solutions or suspensions of antioxidants or by immersion into them, but in some case
it is better to fine spray a solid antioxidant. If a product should be soaked, it is kept for a
long time in a solution of an antioxidant or the antioxidant is introduced into tissues by a
syringe.
Pieces of fatback can be treated by rubbing the antioxidant together with salt in dry
salting, or by adding the antioxidant in solution into the brine in brine salting.

CHAPTER 1

65

Dehydrated products are usually treated with solutions or a suspension of an antioxidant before drying.
Into rendered fats and chopped products, antioxidants and antioxidative compositions
are also introduced in propylene glycol or in mono- or diglycerides; volatile solvents
alcohol or acetic acid can also be used; afterwards they are removed by a combined action
of temperature and vacuum. Salt, glucose and spices can also be used as antioxidant
carriers.
Some Western companies manufacture ready-made antioxidant compositions in
solutions.
The number of countries, in which the use of some antioxidants and synergists is permitted, increases. Recently, the Committee on Food Additives (FAO/WHO) determined the
limits of unconditionally and conditionally permissible daily doses of antioxidants for man.
The largest unconditionally permissible should not be considered as the maximum value, which can be permitted from the point of view of toxicity of a food additive. Therefore,
the Committee found it expedient to set the limits of conditionally permissible daily doses
so that experts in each country could make a final decision on the permissibility of the doses
within the limits conditional for this or that food additive with consideration of special requirements of their own country, groups of population, kinds of food into which additives
would be introduced, methods of their treatment, consumed amount of this food and other
peculiarities.
For some substances, only conditionally permissible doses are given due to the
absence of sufficient scientific data required for the toxicological evaluation of those
substances.
1.4.10 Methods for identification of antioxidants
The following methods are proposed for a quantitative determination of antioxidants, synergists and metal deactivators, as well as their mixtures: polarographic, colorimetric, spectrophotometric (in the visible, ultraviolet and infrared regions of the spectrum),
chromatographic (paper, gas and thin-layer chromatography) and other methods.
Polarographic methods and methods of determination in the infrared region of the
spectrum are not many and found no wide use.
Of considerably greater interest for practical purposes are spectrophotometric methods
of determining antioxidants in the ultraviolet region of the spectrum.
UV spectrophotometry is used for determining butyloxyanisol and butyloxytoluene in
edible fats.
In the presence of PG, BOA, NDGA, citric acid and monoisopropyl citrate, more than
93% butyloxytoluene was determined. Spectrophotometric curves of BOT and other inhibitors are given in Fig. 1.18.
Based on thorough studies of the spectrophotometric method of determining butyloxyanisol, higher and lower gallates in edible fats and oils, the authors consider it the simplest
and most reliable for quantitative determination.
Light absorption is measured at several wavelengths after extraction of antioxidants
by 72% ethyl alcohol. This method also makes it possible to determine the content of ascorbic acid in the presence of the above antioxidants.
A method of determining ethoxyquine in feeds from the absorption in the UV region
of the spectrum has been proposed.
Determination of ethoxyquine is based on its extraction with 0.5N HCl from the sol-

66

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

50

Absorptivity

40

30

20
3

10
4
5
0
240

260

280
, m

300

320

Figure 1.18 UV absorption spectra of antioxidants and synergists: 1, propyl gallate; 2, butyloxyanisol; 3, nordihydroguaiaretic acid; 4, butyloxytolyene; 5, citric acid.

vent and the measurement of the optical density of the solution at a wavelength of 296 m
(Fig. 1.19).
Other spectrophotometric methods of determining antioxidants in the UV region of the
spectrum have been also described.
Colorimetric methods, as spectrophotometric methods in the visible region of the spectrum, are used the most frequently for quantitative determination of antioxidants in edible
fats.
For carrying out the colour reaction, antioxidants are extracted from fat by a suitable
solvent or are distilled with superheated steam (in determining butyloxytolyene).
For quantitative determination of a number of antioxidants: butyloxyanisol, butyloxytoluene, gallic acid ethers, nordihydroguaiaretic acid, tocopherols and others, use was
made of redox reactions. The colour reaction is performed with ,-dipyridyl or potassium
ferricyanide. These colorimetric methods are nonspecific.
A reagent 2,6-dichloroquinone chlorimide is widely used for antioxidant determination; this reagent is specific for butyloxyanisol.
Using 2,6-dichloroquinone chlorimide, the content of butyloxyanisol in the presence
of butyloxytoluene can be determined.
A spectrophotometric method was developed for quantitative determination of gallates. Determination of propyl gallate is based on the colour reaction with the reagent ferrotartrate in the presence of an aqueous solution of sodium acetate and the measurement of
the coloration at a wavelength of 530 m with respect to water. When determining octyl

CHAPTER 1

67

1.0
1

0.9
0.8

Optical density

0.7
0.6
0.5
2
0.4
0.3
3
0.2
0.1

280

300

350

, m

Figure 1.19 UV absorption spectra of a standard solution of ethoxyquine in 0.5N HCl: 1, 0.0112
mg/ml; 2, 0,0056 mg/ml; 3, 0,0028 mg/ml.

and dodecyl gallates, the optical density of the solutions at 550 m with respect to isoamyl
alcohol is measured.
A simple and fast method of determining gallates is based on their isolation from fat
with a 95% alcohol and the determination of the amount of gallates in the extract by
measuring the coloration formed with Mohrs salt, at 580 m.
Recently, a complexometric method of determining antioxidants was developed. Mercury acetate proved the best precipitation agent of gallates. This method yielded good results in determination of gallates soluble in water. At the determination of butyloxyanisol
by the complexometric method the author obtained more reliable data than in the determination by the colorimetric method.
Chromatographic methods make it possible to detect comparatively easily and in many
cases to determine quantitatively several substances at once, if an antioxidant composition
was added into the product assayed.
Using paper chromatography, antioxidants butyloxyanisol and butyloxytoluene can be
separated in the presence of gallates and butyloxyanisol isomers. Three-valent ferrous sulfate or potassium ferricyanide are used as developers. This method enables detection of
0.001% gallate, 0.005% butyloxyanisol and 0.01% butyloxytolyene in pork fat.
When separating a large number of antioxidants in pork fat or margarine, the chromatogram is sprayed with one of the two developers: (i) a 1% alcohol solution of silver nitrate and after drying a 1% solution of ammonia; (ii) a 2% aqueous solution of borax and
after drying a 0.01% alcohol solution of 2,6-dichloroquinone chlorimide. The separation is
done on paper SS20443b or Whatman No 1.

68

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Paper chromatography is used for separation of tocopherols over a period of several


years.
Using paper chromatography, the content of tocopherols in natural oils is determined.
In one-dimensional chromatography, paper is impregnated with zinc carbonate; in twodimensional chromatography, with paraffin. As a developer, ,-dipyridyl is used.
The method makes it possible to separate and determine -, -, -, -, and -tocopherols.
The literature gives results of separating methyl, ethyl, propyl, octyl, dodecyl gallates;
nordihydroguaiaretic acid, butyloxyanisol and butyloxytoluene using descending paper
chromatography. The antioxidants are isolated by 78% ethanol from a solution of fat in
petroleum ether; the extracts are evaporated to dryness and dissolved in ethyl acetate. For
their distribution, a mixture of chloroform with acetic acid (99:1) is used at a saturation of
the chamber with 50% acetic acid. All antioxidants separate well, besides butyloxyanisol
and butyloxytolyene, which have very close values of Rf.
Butyloxyanisol and butyloxytolyene can be separated most suitably by the method of
chromatography on Mitchell paper.
Thin-layer chromatography has found wide use in determination of food additive
owing to the exceptional speed of the analysis with all the other advantages of the chromatographic methods preserved.
Mixtures of pure antioxidants can be easily and quickly separated using thin layer
chromatography on kieselguhr. 2,6-Dichloroquinone chlorimide and diazotized sulfanilic
acid are used as developers. The method is very sensitive and reliable.
A method of quantitative determination of butyloxyanisol, butyloxytolyene, propyl
gallate and nordihydroguaiaretic acid in lard using two-dimensional thin layer chromatography has been described. Antioxidants are extracted with 80% ethyl alcohol and acetonitrile from a solution of lard in n-hexane. Stains are separated using benzene and acetonitrile. The quantitative determination is performed colorimetrically after extracting stains
from the plate.
This method determines the following amounts of antioxidants: BOA, 98101%;
BOT, 96101%; PG, 90101%; NDGA, 8298%. The method enables efficient separation
of butyloxyanisol isomers.
A method was proposed for determining nordihydroguaiaretic acid, propyl gallate,
ascorbyl palmitate, butyloxyanisol and butyloxytolyene in a thin layer on polyamide powder. A mixture of methanol, acetone and water at 3:1:1 or 6:1:3 ratios is used as solvents.
Identification is performed with diazotized sulfanilic acid or phosphoric-molybdic acid.
Ascorbyl palmitate in the presence of other antioxidants can be determined even if it
is present in fats in the amount of 0.0010.002%. Ascorbyl palmitate extracted from fat is
treated with a solution of the sodium salt of 2,6-dichlorophenol indophenol in the presence
of trichloroacetic acid, heated at 70C with a solution of 2,4-dinitrophenyl hydrazine in sulfuric acid. The reaction products formed are extracted with ethylacetate, separated on a thin
layer of silica gel in a chloroformethylacetate (1:1) system. The brick-red band of the
2,4-dinitrophenyl hydrazine derivative of the dehydro form of ascorbic acid taken from the
plate is eluted; the intensity of coloration of the solution is determined photometrically at
520525 m.
Thin layer chromatography can be used to separate methyl, ethyl, propyl, butyl, octyl
and dodecyl esters of gallic acid. A 10% acetylated cellulose is used as the stationary phase;
the solvent is a four-component system of a solution of Shell Soil A, n-propyl alcohol,
glacial acetic acid and formic acid at ratios of 45:6:3:6 (v/v).

CHAPTER 1

0.6

Detector signal, mV

69

0.5
1
0.4
0.3
0.2
0.1
0

10

5
Time, min

Figure 1.20 Chromatogram of a standard solution in petroleum ether: 1, butyloxyanisol; 2, butyloxytolyene.

Thin layer chromatography on polyamide was applied in determination of flavonoids,


glucosides and fat-soluble vitamins.
A number of gallic acid ethers, butyloxyanisol, butyloxytolyene, sesamol and others
were analyzed on a starch-bound polyamide layer in a methanol/acetone/water solvent
(60:20:20).
On a thin layer of polyamide, the Rf values of a large number of antioxidants (methyl,
ethyl, propyl, butyl, octyl, dodecyl gallates; butyloxyanisol, butyloxytolyene, sesamol, nordihydroguaiaretic acid, ascorbyl palmitate) with various solvents (methanolacetone
water, 60:20:20 and light petroleum etherbenzeneacetic aciddimethylformamide,
10:10:5:0.25) were determined.
The development of gas chromatography provided for the possibility of its use in the
field of antioxidant determination.
A method using gas-liquid chromatography has been developed for separation and
quantitative determination of butyloxyanisol, butyloxytolyene and ethoxyquine in samples
soluble in water and hydrocarbons. In combined occurrence of all of these antioxidants,
they are determined at a temperature of 188C on a column (1520.6 or 0.3 cm) filled with
20% silicon SE-30 on refractory brick (6080 mesh) at a helium flow rate of 185 ml/min;
detection, by heat conductance.
To determine traces of BOA, BOT and ethoxyquine, it is recommended to perform
chromatography at 185C on a column filled with 20% silicon SE-30 on chromosorb W at
a gas flow rate of 175 ml/min. An ionization detector is used.
For a quantitative determination of butyloxytolyene and butyloxyanisol in dehydrated
potato granules, a fast method of gas-liquid chromatography using a flame ionization
detector has been proposed. Figure 1.20 shows a chromatogram obtained in determination
of a mixture of both antioxidants.

70

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

A combination of rapid extraction with a gas-chromatographic assay enabled determination of traces of butyloxytolyene and butyloxyanisol in potato granules, vegetable oils
and packaging materials. The use of a column with a mixture of silicon SE-30 and Tween
80 at 150C provided a possibility of complete separation of assayed substances from interfering impurities. 3,5-Di-tert-butyl-4-oxyanisol was used as an internal standard.
A method of determining butyloxyanisol and butyloxytolyene on a gas chromatograph
with temperature programming and use of 3,5-dibutyloxyanisol as an internal standard has
been described. A chromatograph equipped with a catharometer was applied. Initial temperature of the column, 125C; final temperature, 190C; programming rate, 11 deg/min.
All existing methods of determining antioxidants, besides gas-liquid chromatography,
are low-sensitive at antioxidant concentrations below 1 mg%.

2
2.1

Polymer Packaging
Materials for Preservation
of Foodstuffs

Food polymers

One of the most important high-molecular-mass compounds is at present the class of polymers. As compared with common substances, such as, e.g., water (molecular mass, 18),
benzene (molecular mass, 78), chalk (molecular mass, 100), the values of polymers
molecular masses vary within the range of tens of thousands up to millions. In polymers,
their giant molecules are built from consecutively bound groups of atoms forming a long
chain, which contains sometimes hundreds of thousands repeating structural units: elements, links. The word polymer means many parts and is derived from the Greek words
polys meaning many and meros meaning parts. An example of a polymer consisting of atoms linked by chemical forces into a chain is plastic sulfur. As is known, it is produced by pouring molten sulfur into cold water. The structure of polymer sulfur is
S S S S . In this
represented by a chain of atoms linked by chemical bonds:
state, the properties of sulfur differ from the properties of common crystalline sulfur. They
resemble rubberlike rather than solid bodies. For most polymers, the repeating elements of
the structure are usually small groups of atoms. One of the simplest (from the point of view
of its chemical structure) and widespread polymers polyethylene has the following
structure: CH2 CH2 CH2 CH2 CH2 ... .
Polyethylene is obtained by attaching molecules of ethylene CH2 CH2 to one
another. By means of corresponding catalyst and conditions, the double bonds are opened
and chains are formed from consecutively attached groups of CH2 CH2 . The initial
molecule, from which the polymer is formed, is called monomer. The word monomer
is derived from the Greek word monos meaning single. The number of monomer units
forming the chain molecule of the polymer is called the degree of polymerization. Another
widespread polymer, polypropylene, has a close structure:
...CH2

CH
CH3

CH2

CH
CH3

CH2

CH
CH3

It is obtained by attaching molecules of propylene CH2

CH2

CH

...

CH3
CH to one another.

CH3
As polyvinyl chloride ... CH2 CHCl CH2 CHCl CH2 CHCl ... obtained
by polymerization of vinyl chloride CH2 CHCl , polyethylene pertains to large-scale

72

products.
...
CH2

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Large-scale polymers include synthetic rubbers (polyisoprene


C CH CH2 , butadiene ... CH2 CH CH CH2 ... , and others),

CH3
polystyrene ... CH2

CH

CH2

... , cellulose hydrate and esters, as well as poly-

CH

mers, which are used in contact with foods. Among polymer materials suitable for contact
with food products, of special importance are linear polyesters, whose links contain aromatic and aliphatic groups, e.g., polyethylene terephthalate or polyethylene glycol terephthalate ...OCH2

CH2OOC

CO

... .

This is a crystallizable polymer. Its polymerization rate is maximal at 180190C. It


does not crystallize below 97C. Crystallites of polyethylene terephthalate melt at 256C.
If the melt is rapidly cooled, it has no time to get crystallized and will be in a glass-transition
state. The temperature at which it begins to pass from the glass-transition to rubber-like
state is 81C. If, however, the polymer has time to get partially crystallized (at a slower
cooling), its glass-transition temperature increases. Thus, for instance, at the crystallinity
rate of 65% the glass-transition temperature increases up to 120C.
Films from polyethylene glycol terephthalate are 5 to 6 times stronger than oriented
films from polyethylene, possess a lower vapour and water permeability and a larger oxygen and light resistance.
The breaking strain of this film is 175 MPa; relative elongation, 5070%; lowtemperature resistance, 160C; water absorption, 0.5%; melting temperature, 250C; temperature of the total strength loss, 248C.
O
If the main chain of the macromolecule contains amide groups C NH , then the
polymer belongs to the class of polymer compounds under the general name polyamides;
in a general form, their chemical structure can be expressed by the general formula
...

C
O

NH

R'

NH

...

where R and R are meant to be atomic groups ( CH2 )n and (CH2)m. Films from polyamides in combination with films from other materials have recently found use in packaging of meat products.
Along with the required performance properties, such as chemical durability, a certain
level of the physicochemical, physicomechanical and technologocal properties, polymer
materials used in direct contact with foods should also meet high hygienic requirements.
Therefore, in accordance with the law, polymer materials can be used in contact with a
given type of food products only after a corresponding permission from the sanitaryepidemiological bodies. Goods from polymers are subject to thorough organoleptic,
sanitary-chemical and toxicological studies.
Polymers are produced not only by chemical methods. They are widespread in nature
in the form of cellulose, starch, natural rubber, silk and various resins. Not only many kinds
of natural polymers can be reproduced by chemical methods and synthetic polymers

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73

developed (e.g., synthetic rubber), but also new polymer substances required for the economy can be created. Chemical methods can also be used to change the chemical nature of
a natural polymer, e.g., cellulose, by imparting it with the required properties. As a rule,
natural, synthetic and chemically changed natural polymers are used not in pure form, but
in various combinations both between themselves and with various substances added into
the polymer composition to impart it with properties required.
To date, there is a tendency not to expand the range of large-scale polymers used as
the basis for production and processing of plastics, but to search for rational ways of using
traditional polymers. This search proves the most productive in physicochemical, chemical
and physical modification of polymers or in combining various polymers and other materials in constructions, which optimally combine the properties of a component and the final
complex of the properties of material or article.
The simplest variant is a mixture of two or several polymers, which gives the required
combination of performance properties.
When choosing a polymer for fabricating an article, one should proceed from the purpose of the article and conditions of its use. Herewith, one should be based on the values of
the characteristics, which determine the performance of the article, e.g., the value of breaking strain at the sterilization temperature or the strength of an adhesion seam in heat sealing
etc. These characteristics should correlate with conditions, under which the article would
be operated, e.g., the value of strength should not go below a given level under all performance conditions. The successful fabrication of an article from polymers is possible only
if the characteristic properties of the plastics are taken into account depending on the operational conditions and methods of processing.
When choosing polymers, it is necessary to use their resources to a maximum, so that
an article not only conforms to its purpose but its fabrication from a chosen plastic is economically more expedient than fabrication from another material. The chosen polymer and
other ingredients of a composition should conform to the sanitary-hygienic conditions.
Most polymer compositions used to produce plastics can include besides a polymer
binder hardeners, plasticizers, fillers, dyes, pore formers, lubricating agents and other
components. Each of the components of a polymer composition performs its specific
function.
Plasticizers are usually introduced into plastics to increase the plasticity of a composition and of a plastic produced from it. This change of properties (physical modification)
contributes to an easier processing of the plastics into articles, increases their low temperature resistance, decreases the elasticity modulus. Introduction of plasticizers into a composition facilitates the mixing of a polymer with other ingredients, decreases the
temperature of processing a plastic into articles. In some cases, besides the above functions
plasticizers also impart plastics with such properties as, e.g., noncombustibility, increases
their heat resistance and light permanence.
Both low- and high-molecular-mass compounds can serve as plasticizers. The requirements they should meet are as follows: the ability to match with polymers to form an operationally stable system, low volatility; absence of colour, smell; the plasticizing action
should be preserved at the lowest operational temperatures; chemical stability should be no
less than in polymer components.
In some cases, additional requirements should also be met, such as an almost complete
absence of extractability from the polymer with liquid media, oils, solvents, detergents,
food products.
The most important plasticizers include esters of aromatic and aliphatic carboxylic

74

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

acids and phosphoric acid, epoxidized compounds, polyesters, esters of glycols and monocarboxylic acids.
Fillers of plastics are solid and gaseous substances, whose introduction makes plastics
stronger, less deformable and less shrinkable, or makes them to acquire other useful properties, such are incombustibility, larger friction coefficient, electrical conductivity etc. In
some cases, fillers do not improve the operational properties but, being a cheaper and more
available part of the plastics, reduce their cost. Fillers, which significantly improve the
operational properties of plastics are usually called active.
The content of fillers in plastics can change within broad limits and is usually 4550%
in terms of polymer weight. In high-filled plastics, the content of filler can exceed the polymer content severalfold.
Of undoubted interest are the current works on production of high-filled thermoplastics directly in the synthesis process. The idea is to use the catalyst applied onto the carrier as a filler in the polymer composition. Thus, the filled composition is produced directly
in the reactor, which not only makes the mixing process simpler, easier and less energyintensive, but contributes to a stronger bonding between the components. Such materials
developed by academician N.S. Enikopolov et al. were given the name of norplastics.
The most widespread fillers are solid; they are divided into powdery and fibrous. In
some cases, such fillers as, e.g., graphite, glass, various metals etc., are used both as powders and fibres. Active fibrous fillers are called reinforcing fillers.
The general requirements imposed on fillers are primarily their ability to mix with
polymer to yield a given degree of homogeneity, the ability to be wetted by the polymer
melt or solution, the stability of the properties in storage of the filler, processing and use of
the plastic.
When using powdery fillers, the process engineer should solve a number of problems,
such as to determine the optimal size of particles, the concentration of filler and the desirable structure of the polymerfiller system. In the latter case, it is desirable to determine
which type of structures (a more or less uniform distribution of particles in the bulk of the
polymer composite, or formation of chain structures consisting of filler particles, or else,
e.g., formation of a three-dimensional network from the chain structures etc.) is the most
expedient for achieving a given set of properties.
It follows from the above that polymer materials are used in fabrication of articles not
as individual substances but as a polymer composition, a mixture of various polymer ingredients, which confer a required shape upon the article and then fix this shape by various
technological techniques.
A great diversity of polymer types and polymer compositions makes it possible to
choose those the combinations of properties of which correspond to the conditions of operation of an article. Especially specific are operational conditions of polymer materials
used for packaging of foods. Packaging is reduced to not only providing the possibility of
prepackaging and transporting the food products, but to protecting them from the impact of
the environment, pathogenic bacteria, preserving the nutritive value of a product, increasing
its expiry date and many other aspects. Thus, a polymer packaging is active with respect to
a food product. However, this activity can be not only useful but also harmful.
This is due to the fact that polymer material is a complex composition, which, besides
a polymer, i.e., a high-molecular-mass compound, includes many low-molecular-mass
chemical compounds.
As a rule, additives and low-molecular-mass impurities are chemically not bound to
the polymer. Under certain conditions, these substances can pass (migrate or diffuse) into

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75

the contacting medium: air, water, foodstuffs. This creates a potential hazard for man when
using polymer materials as food packaging, because migrating substances can be toxic and
have adverse effects on the human organism. Of special importance is that, getting into the
human organism in small concentrations but acting for a long time, they can evoke no fast
and acute diseases, but act slowly and sometimes not manifesting themselves for years.
Therefore, prevention of such pathological phenomena becomes the most important
hygienic and social problem.
This problem is being solved by a common effort of physicians, chemists and process
engineers. At present, physicians listen to a course of lectures on polymers, and process engineers study the possible consequences of incorrect use of polymer materials and methods
of developing practically harmless polymer articles.
The hazardous action of polymer articles is usually determined by the toxicity of lowmolecular-mass substances present in them, but not by the polymer itself, which is practically insoluble in water and other food media. Therefore, two criteria determine the harmfulness of a polymer material: the toxicity of low-molecular-mass substances present in a
polymer or forming in it, and the amount of these substances passing into the contacting
medium. The certificate of toxicity, i.e., the extent of harmfullness for man, of chemical
substances is issued after toxicological studies; and the chemical composition, amount and
character of migration of individual substances from polymer materials are studied in the
course of sanitary and chemical tests.
In view of the importance of this problem, besides a certain set of physicochemical and
physicomechanical properties, polymer materials intended for contact with foods should
also satisfy hygienic requirements: the formulation of a polymer material should not include
substances possessing a toxicity, but only those substances that are permitted by the Ministry of Health bodies and are present in a corresponding list; articles from a polymer material in contact with food products should not change their organoleptic properties (i.e.,
taste and smell) and should not evolve low-molecular-mass chemical substances in amounts
exceeding admissible levels, i.e., in amounts, which can have a harmful effect on humans
when taken up with food; at the impact of food media, the appearance of the articles should
not change. Physico-hygienic, physiologo-hygienic and microbiological studies can be also
necessary in some cases.
2.2

Hygienic characteristics of packaging materials components

Preliminary information on the hygienic characteristic of substances introduced into a polymer composition can be obtained based on the physicochemical properties solubility in
various media, volatility etc. However, ultimately the possibility of using this or that chemical substance in polymer materials can be decided upon only based on the data obtained in
experiments on animals. The aim of toxicological studies is to reveal the toxic action of
low-molecular-mass substances, evolved from polymer materials into the environment, on
the animal organism. The currently accepted scheme of toxicological studies is two-stage.
The first to be studied are the toxic properties of separate components, which are either initial substances for producing a polymer or are introduced into it subsequently to impart it
with certain properties. In each particular case, the need for the toxicological evaluation of
substances is determined based on the formulation of polymer material and the results of
the sanitary and chemical analysis. This toxicological evaluation is to establish the norms
of evolution of these low-molecular-mass components into the environment air, water,
food products or model media imitating them. If, as the result of a toxicological evaluation,

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

any of the additives is found to be practically nontoxic, no norms of evolution for it are established, and its use is permitted in all-purpose plastics without any obligatory control of
its evolution.
The second stage of the toxicological evaluation is to study the toxic action of all polymer material as a whole depending on its assumed application. This type of toxicological
research is to be carried out either when the evolution of separate components is close to
the established norms but the combined action of several components is anticipated to be
stronger, or when not all substances evolved from the plastic have been identified. It is especially important in this case to establish the amount of substances capable of evoking a
pathological effect.
Proceeding from the degree of the risk of possible pathogenic effects on the organism
to develop, taking into account the biological activity and extent of migration from polymer
materials, various additives can be divided into admissible, whose use for food brands of
polymer materials is permitted, and inadmissible.
The first group includes compounds, which do not change the organoleptic properties
of products, and also those whose harmlessness has been proven by many years of practice.
This group includes most major compounds used in production of polymer materials:
monomers, plasticizers, dyes. However, their use is regulated by hygienic norms the admissible amount of migration (AAM) (e.g., for such monomers as styrene, epichlorohydrin,
formaldehyde) or by standardization of their content in a polymer composition on the level providing for the harmlessness for foods.
The group of inadmissible compounds includes those the use of which in production
of food-purpose polymer materials is totally banned.
This group incorporates compounds, which possess a high toxicity and pose a significant threat in the case of migration into the environment (e.g., arsenic and lead compounds).
Based on the results of hygienic studies, the maximally admissible daily dose (Dm) is
established.
This coefficient is a major parameter for the calculation of the AAM for a given substance in the food brands of polymer materials.
Based on the results of the toxicological experiment of determining Dm and AAM, the
health bodies make a decision on the admissibility of using the substance studied in food
brands of polymer materials.
Let us dwell on the evaluation of the biological activity of compounds used the most
in production of polymer materials: monomers, catalysts, initiators, stabilizers, plasticizers.
Monomers. When producing polystyrene, the initial monomer is styrene (vinyl benzene) a liquid with a characteristic smell, which boils at 146C. The norm of the admissible amount of migration of styrene from polystyrene articles is 0.01 mg/l.
Epychlorohydrin is a colourless transparent liquid with a specific irritating smell. Possesses a high biological effect, which to a large extent is explained by the presence of chlorine-containing groups in the molecule. AAM of epychlorohydrin is 0.1 mg/l.
Vinyl chloride is a colourless gas without a smell; boils at 13.8C. AAM of vinyl chloride is 0.01 mg/l.
Most polymerization catalysts are totally incorporated into the final product. The residue of the inorganic compounds in the polymer can be characterized by the ash content.
Thus, the ash content of polyethylene intended for contact with foodstuffs should not exceed 0.02%. The presence of even insignificant amounts of catalysts in the finished article
may lead to a faster ageing of polymer material.

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77

Polymerization initiators are capable of decomposition during the heating to form free
radicals. Usually, oxygen-organic and -inorganic peroxides, hydroperoxides and diazo
compounds are used as initiators. Most of these substances possess an irritating action, have
an effect on the nervous system. Peroxide degradation products are also biologically active.
The content of polymerization initiators and products of their degradation in finished polymer materials should not exceed 0.2%.
Stabilizers contribute to the long-term preservation of the properties of plastics. Stabilizers enter into a chemical interaction with polymer. They readily diffuse from it into
contacting media. The proximity of the mechanisms determining the efficiency of stabilizers to the phenomena occurring in a living organism points to their biological activity.
Widespread heat stabilizers are stearates of metals calcium, zinc borate, lead etc. Calcium
and zinc stearates, as well as complex stabilizers, proved to be practically nontoxic substances. At the same time, stearates of cadmium, barium, lead possess a high toxicity.
For stabilization of PVC materials contacting with foodstuffs, epoxidized soybean oil
is used, which is a low-toxic compound. However, its introduction to the polymer composition in excess amounts may enhance migration of the other ingredients.
Plasticizers. All in all, 2000 various plasticizers are known; however, in production of
materials contacting with food products, a limited number is used: glycerol; paraffin oil;
ethanolamines; esters of phthalic, sebacinic, adipic and citric acids; as well as lowmolecular-mass polyesters. In the opinion of some investigators, esters of sebacinic and citric acids, as well as stearic acid and its salts (calcium and zinc stearates) can be considered
to be practically nontoxic plasticizers.
Glycerol, triacetin, castor oil, mono-, di- and triethanolamines and their salts are also
attributed to nontoxic plasticizers. Of great importance are acetyl tributyl citrate and ethylhexyl phenyl phosphate, which are used to produce films intended for packaging of food
products. Both plasticizers are low-toxic, possess a high water, oil and low-temperature resistance as well as insignificant volatility.
Fillers. Silicon dioxide, chalk, cellulose, wood veneer, titanium dioxide etc. are used
as fillers. For the most part, they are nontoxic.
Solvents. Organic solvents toluene, benzene, ethylacetate, hexane, petrol, methylene
chloride etc. are used in polymerization or polycondensation in solution. Certain amounts
of these solvents can remain in fabricated polymer materials both after the main process
operations and after some auxiliary operations. Chloroorganic and aromatic compounds
and alcohols can remain in the material owing to incomplete drying.
Migration of solvents into contacting media can have an impact on their taste and
smell, and also lend them toxic properties. Information on the toxicity of particular solvents
can be found in reference books PDK Vrednykh Veshchestv (=MPC of Harmful Substances) (in Russian) (Leningrad, Khimiya Publishers, 1975) and Vrednye Veshchestva v
Promyshlennosti (=Harmful Substances in Industries) (in Russian) ed. by N.V. Lazarev
(Leningrad, Khimiya Publishers, 1971).
Dyes. Synthetic or natural dyes soluble in most common solvents, as well as pigments
of organic and inorganic origin are used for colouring plastics. The dyes are usually insoluble. Migration of dyes can have a general toxic action during its penetration through the
skin, as well as in the stomach during its intake with water or with food products.
Various aminoanthraquinone and azo dyes are capable of evoking disturbances of the
functional state of the liver, kidneys, the central nervous system; to disturb redox processes
in the organism. A characteristic feature of most dyes is a low toxicity at a single introduction into the organism in large doses and the ability to cause intoxication during the chronic

78

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

intake of small doses.


As for inorganic dyes, their biological activity depends on the element occurring in the
compound. A general toxic action is characteristic of strontium- and chromium-based dyes.
Iron- and titanium-based dyes are practically harmless. To guarantee the harmfulness of
using coloured articles, the AAM for dyes is set to be with the safety margin of 1001000.
In operation of polymer materials, they age, i.e., their physicochemical and physicomechanical properties change under the action of external conditions. Ageing of polymers
is due to the degradation reactions owing to the rupture of the molecular chain. As the result
of the degradation, articles get deformed, crack and in some cases break. Some degradation
processes are accompanied with a change of the appearance of the articles, staining, yellowing, blooming, warpage etc.
Degradation of polymers usually occurs under the action of chemical agents (water,
alcohols, acids, oxygen, ozone etc.) or under the action of physical impacts (heat, light, ionizing radiation, mechanical energy etc.). Polymers can also be degraded during their processing owing to the violation of the technological regime. All these processes are
invariably associated with the evolution of harmful chemical substances degradation
products from plastics into the environment.
Decomposition of polyethylene is accompanied with evolution of such substances as
formaldehyde, acetaldehyde, acids, unsaturated hydrocarbons, low-molecular-mass oligomers; in strongly pronounced decomposition, H2O and CO2 can evolve. Besides the above,
acetone, methyl alcohol and other alcohols are found among the degradation products of
polypropylene.
The most toxic are formaldehyde its AAM was set to be 0.1 mg/l and methyl alcohol (AAM, 1.0 mg/l).
Polystyrene in degradation evolves styrene, -methyl styrene, ethyl benzene and other
aromatic hydrocarbons, benzaldehyde, benzophenone and other aromatic aldehydes and
ketones. Aldehydes, alcohols, hydrogen chloride, chlorinated hydrocarbons, unsaturated
hydrocarbons are formed as the result of the degradation of PVC.
Ageing of methylacrylate is accompanied by the evolution of methyl alcohol, MMA,
methacrylic acid, unsaturated hydrocarbons. The AAM of MMA is 0.25 mg/l.
Amino plastics are degraded to form aldehydes (formaldehydes), ammonia; phenoplastics, to form phenol (AAM, 0.001 mg/l), aldehydes; epoxy resins evolve epichlorohydrin (AAM, 0.7 mg/l), phenol, chlorinated hydrocarbons, aromatic hydrocarbons. To
predict the potential hazard of plastics used for contact with foodstuffs, it is necessary to
have a real idea of the chemical nature of substances evolving from them, the level of their
migration and toxicological characteristics.
To establish the correspondence of the finished article to the hygienic requirements,
special studies should be carried out. They are based on modelling the real conditions under
which polymer materials would be used, followed by the determination of the organoleptic
properties of the contacting media and the level of migration of the chemical compounds.
In an ideal case, migrating substances should be determined directly in food products.
However, the compositions of food products are rather complex, so in most cases it is
impossible to determine particular chemical compounds in them. For instance, milk is a
complex chemically and biologically active system, which includes protein, fat, plasma;
these, in turn, consist of amino acids, casein, albumin etc. The presence of these substances
not only disturbs the determination of separate compounds migrating from plastics, but is
also capable of changing the initial shape of these substances, i.e., to enter into interaction
with them. Nevertheless, a number of highly sensitive assays for determining separate low-

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79

molecular-mass substances in food products (e.g., solvents, plasticizers, monomers in sunflower oil, milk, curd, cheese) have been developed to date; still, sanitary-chemical studies
are mainly carried out on model solutions, which simulate particular kinds of products by
the most characteristic features.
Solutions of some salts, acids, alcohols serve as model media to simulate the extractability of various food products. In all cases, water is used as one of the model solutions as
the most universal and convenient medium for organoleptic studies and the determination
of the amount of chemical substances migrating from plastics.
Different countries use various sets of model media, which reflect more or less completely the character of major food products. An essential criterion in choosing a model medium is to simulate the factors, which contribute to or prevent the migration of chemical
substances: the consistence of a product, its pH and composition of the salts; the content of
water, fat or alcohol. The greatest attention is paid to liquid and fatty products.
The requirements to plastics used for prepackaging solid food products are less stringent. In some countries, they are permitted to be used without special studies.
In the Russian Federation, 9 model media are used; in the USA, 8; in France, 13; in
Czech Republic and Italy, 6; in Germany, 4. There are certain differences in the composition of model media simulating the same food products, especially of fats, which are proposed to be replaced in tests by olive or sunflower oil, heptane, hexane, diethyl ester.
It is known that aggressivity of food products with respect to polymer materials depends to a certain extent on the content of moisture in them. Therefore, the approaches to
the studies of articles intended for contact with food products of a moisture content of above
15% and below 15% are different.
Almost all model media include water, so for simplicity water-containing products are
simulated by water; fat-containing products, by sunflower or other vegetable oil. As the result of accumulation of experimental data, the principles of choosing simulators of food
products are being reconsidered at present.
The conditions of modelling polymer tests in this country have been accepted to depend upon real conditions of their practical use with some exaggeration.
The specific surface of specimens of a material or articles should correspond to real
operating conditions.
The sanitary-chemical study is preceded by organoleptic studies. Their aim is to reveal
the possibility of transferring a foreign smell and flavour to food products, which are in contact with a polymer material. The organoleptic parameters are determined by tasting and
are expressed in points of smell intensity. Changes of the organoleptic properties of food
products and model solutions contacting with articles studied are due to the transition of
polymer components into them. In this connection, the data obtained in the organoleptic
studies are one of the most important limiting parameters in the sanitary-chemical study of
articles from polymer materials. If the organoleptic examination reveals a change of smell
and taste of a food product or a model medium as the result of a contact with polymer material, this is the reason for banning this material for packaging foodstuffs.
The subsequent sanitary-chemical studies isolate both the total amount of substances
that passed into model media from the polymer composition, and separate components.
Their qualitative composition is determined, i.e., chemical substances are identified and the
character of their migration is defined. The total amount of low-molecular-mass substances
that pass into the media is determined by the so called integral methods. They include the
methods of oxidizability, brominability, dry residue of the extracts. However, neither of the
methods gives the complete idea of all substances migrating into model media. In particular,

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

the oxidizability shows the total content of (organic and inorganic) reducers (in solution)
capable of oxidation under conditions of the experiment, and characterizes the resistance
of the material to water. The brominability testifies to the presence (in extracts) of substances capable of adding bromine, e.g., unsaturated compounds, phenol. The dry residue obtained by evaporation of the extracts at 100105C contains no volatile substances, whose
boiling temperature is lower than these temperatures.
Therefore, major information in sanitary-chemical studies is obtained using the methods that make it possible to determine the migrating substances in a differentiated manner.
These methods include specific chemical reactions, which make use of the ability of
each individual compound to enter into interaction with certain reagents. Usually, such reactions are used, which yield coloured compounds absorbing light in the visible region of
the spectrum. Such a feature of these compounds makes it possible to register the intensity
of the coloration on a photoelectrocolorimeter type of instruments, and, therefore, to determine the concentration of an analyzed substance with greater accuracy.
Such instrumental methods as gas-liquid and thin-layer chromatography, spectroscopy
in the ultraviolet and infrared regions, mass spectrometry, spectrography are also widely
used.
Much attention is paid at present to the elucidation of the regularities of migration of
individual supramolecular components, which is especially important for packagings and
containers for long-term use. In a general case, the intensity of migration is affected by the
physicochemical impact of polymer and medium, the composition and technology of producing and reprocessing a polymer, duration of contact of the product and the packaging.
The migration ability of particular components is described using the diffusion equation,
which gives a possibility of predicting the migration process at different operating conditions. Migration of monomers is well described by the diffusion equations, as in this case
the determining factor is the solubility of the monomer in the polymer.
In a number of cases, migration processes of additives are described by two parameters: D (diffusion coefficient) and S (solubility). When an additive in the model medium is
not very small, migration is determined by diffusion of the polymer additive and changes
proportionally to time raised to the power of 1/2. When additives are very small, the rate of
migration changes linearly.
In a number of cases, the migration process is described taking account of several factors (concentration of a component, temperature of the medium, time of contact), by making
up the regression equation. Mathematical models of migration of this or that component are
being developed.
The chemical nature of the model medium has a significant effect on the character of
migration. It has been found that water, weak solutions of acids and salts evoke a surface
cracking of PE at elevated temperatures, which leads to accelerated migration of lowmolecular-mass substances from these materials. In this connection, the use of such a material as PE should be limited in time at temperatures higher than 60C due to possible
cracking. The amount of migrated substances (solvents, products of heat-oxidation decomposition) often does not exceed the admissible level of migration. However, it deteriorates
the organoleptic properties of food media, which is also inadmissible from the hygienic
point of view.
An insignificant swelling in fats or fat-simulating media is not always a sufficient reason for recommending a material as a packaging for fat. In a number of cases, the determining factor is oxygen permeability of the polymer film, because an increased oxygen
permeability leads to a rancidity of the packaged fat-containing product, as well as to a

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81

decrease of vitamins in it. Besides, one should pay attention to the fat solubility of polymers low-molecular-mass ingredients: plasticizers, stabilizers, dyes. Only consideration of
all the above factors together enables a conclusion of the expediency of using a particular
material in contact with fat. Owing to a change of its composition, the same polymer can
be used in different applications. One of the oldest polymer materials cellophane has
been widely used in the recent years as a packaging for foodstuffs (owing to its low hydrophilicity and gas permeability due to the application of a lacquer coating on the surface of
the film). This material can be heat sealed, so cellophane can be used as casings for sausages
and cheeses. But new problems have arisen: removal of the residual solvent in the lacquer,
especially from the adhesive layer, the purpose of which is to create a strong bonding of the
coating and the film. If the coating is formed directly on a product, one should take account
of the diffusion of the solvent not only in the air but also in the product. Thus, when applying
a latex coating on a cheese, the residual content of the solvents and monomers is controlled
both in the coating and in the cheese. The sanitary-chemical properties can be improved and
the range of application of the material could be expanded not only by changing the composition of the polymer material, but also by varying particular parameters of the technological process. For this purpose, the technological process is to be optimized with
consideration of definite sanitary-chemical parameters of significance for a given material.
This approach was used to modify the process of producing a combined material based on
polyethylene and cellophane. Besides the major technological parameters, the mathematical model of the process comprised the organoleptic parameter, which is the determining
parameter in this case, and the extent of oxidation of the polyethylene coating surface.
Mathematical treatment of the data made it possible to choose the temperature of PE extrusion on cellophane, at which the organoleptic and other sanitary-chemical parameters of the
material satisfy the generally accepted hygienic norms. The sanitary-chemical properties
often become a determining factor in deciding which of the materials is in this case the best.
The criterion of choosing the material has been developed, which takes into consideration the sanitary-chemical parameters. This criterion is the ratio of the aggregate of the useful properties to the total costs of all the life cycle, which adds up from the expenses for
development, production and operation. This or that hygienic parameter (e.g., oxidizability,
content of solvents, temperature at which a smell emerges) is assigned a certain numerical
value in the abstract scale (1 or 0) and the sum of values for one and the other material is
calculated. For instance, LDPE and HDPE are compared with respect to oxidizability (less
for HDPE), number of solvents (available for HDPE), migration of 3,4-benzpyrene (less in
HDPE), smell (appears in HDPE at a higher temperature). At the same costs, the preferred
material should be HDPE, whose complex parameters of the hygienic properties are 20%
higher than those of LDPE.
Owing to the studies carried out in the recent years, the quality of many polymer materials was significantly improved.
The major way of achieving this are:
increase of the purity of initial raw materials
introduction of nontoxic additives into the composition
selection of the formulations of polymer compositions, which ensure a sufficient
chemical stability of materials
choice of optimal polymer-processing regimes, which prevent the thermooxidative
degradation of material
application of coatings, preventing migration of low-molecular-mass substances, on

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the surface of material


use of additional technological techniques improving the hygienic properties of materials (vacuum treatment, heat treatment, washing etc.).
It is very important that the technological protocol be strictly observed: ingredients of
the composition should not be replaced by others; raw materials should be of the extent of
purification required to produce a hygienically flawless material. The article obtained
should be used only for the intended purpose within the temperaturetime limits required.
The permit issued by the Ministry of Health stipulates the operating conditions of material
or fabricated packagings, and the violation of these recommendations is fraught with
serious consequences for human health.
Having obtained the results of the sanitary-chemical study, the hygienists make a conclusion of the possibility or impossibility of using the polymer material in contact with given products. If it can be used, the operating conditions are stipulated, i.e., the temperature
regime and time interval, as well as specifically the kind of a food product. The same polymer can be suitable for one product and can not be used in contact with another product.
This is explainable by the chemical nature and physical structure of both the polymer itself
and additions in its composition. Such a widespread material as polyethylene is broadly
used for contact with water-containing products, but on a limited scale with fat-containing
materials. And such a polymer as polyamide is intended for fatty products and can not contact with water. It should be noted that there are many ways to modify polymers: impart
them with water resistance or, vice versa, water solubility, fat resistance, gas impenetrability etc. Due to the latter, materials not used previously for certain products can withstand a
contact with them without changing their properties and the properties of the product. Thus,
for instance, the higher homologs of polyolefins possess an increased fat resistance; application of lacquers on cellophane imparts it with water resistance, while coating polyethylene with foil makes it gas-impermeable.
Unsatisfactory sanitary-chemical parameters are a signal for process engineers, who
correct the production process for polymer articles, change the composition of polymer material, choosing such additives, which would not migrate during the contact of the packaging with the contents. When developing new polymer materials, the technological process
should be optimized with account for the hygienic requirements, and this is a guarantee of
the safety of using polymer materials for food packaging.
At present, all regulatory documents for polymers intended for contact with food products include compulsory hygienic parameters, in accordance with which the material is controlled at the stage of its final fabrication.
2.3

Methods of packaging foodstuffs

To preserve a product, it should be packaged in good condition. If it was getting spoiled,


the very perfect packaging would not restore its original properties. Contrarywise, favourable conditions for accelerated spoilage of the product can develop in the packaging. Thus,
for instance, each variety of fruits and vegetables has its most favourable harvest time.
Fruits and vegetables picked up too early do not reach their normal size. Their green
pulp has a grass acidic taste. The coloration and aroma of these fruits and vegetables are
weakly expressed. If prematurely picked fruits and vegetables are put into storage, they
droop and brown faster.
On the contrary, fruits and vegetables harvested too late are infected with various

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diseases and fungal rots. They are susceptible to damage, cold injury, development of floury
texture, have a tendency of rapid overripeness, loss of gustatory properties and vendibility.
On the strength of the above reasons, it is inappropriate to preserve fruits picked later than
the admissible harvesting time. They should be delivered to the consumer as soon as
possible.
The optimal time of harvesting many varieties of apples could be determined by their
colour. Thus, for long-term storage of many varieties of apples they should be picked when
they have a greenish-yellowish coloration with predominant green colour. Fruits intended
for mid-term storage have yellow-green colour, and totally yellowed fruits are not to be
stored.
The strength of attachment of fruits to the fruiting branch is also an indicator of their
ripeness. Overripe fruits are detached by a weak touch.
Experts determine the optimal time of picking fruits by the colour of seeds, content of
sugar and acid in them, taste and density of fruits and vegetables, content of starch etc.
Any damage (punctures, injuries, damage caused by codling moths and scabs, absence
of fruitstalk) are undesirable in putting fruits into storage. In accordance with the State Standards, only highest and first grade fruits are put into long-time storage. Though harvested
fruits and vegetables receive neither water nor nutrients, they absorb oxygen, evolve carbon
dioxide, water, heat and various volatile organic substances. This physiological process is
generally called respiration. The respiration intensity can also serve one of subjective parameters of ripening, ageing and possible duration of product storage. To make clearer how
the respiration intensity change data are used in such cases, consider an example of storing
apples at various temperatures. First of all, let us mention that it is customary to divide the
change of respiration intensity in the fruit ripening period into three phases. The first is characterized by a low level of respiration. The second is characterized by an increased intensity
of respiration. An increase of respiration intensity implies that fruits have ripened. Subsequently, ageing and spoilage of products shall follow. Spoilage begins the sooner the more
intensive the respiration process is. As is usual, the rate of reversible chemical reactions can
be regulated by either changing the temperature or by changing the concentration of final
products in the reaction medium. Therefore, by decreasing the temperature to some limits
or by changing (modifying) the atmosphere, in which the biologically active products are
stored, we can extend the time during which they achieve optimal properties, i.e., extend
the storage time and improve the quality of the products.
Fresh fruits and vegetables are valuable foodstuffs, one of the major sources of providing the human organism with vitamins, mineral salts, organic acids, biologically active
substances essential for life. The output of these products increases each year; however,
their consumption is obviously of seasonal character.
Partly, the problem of long-time storage is solved by using special chambers and storage facilities at a relatively low temperature of refrigerating chambers with artificial refrigeration.
However, storage of fruits and vegetables in refrigerators has a number of disadvantages: losses are still high; storage is possible only to January or February, only some varieties preserve the food merits in the spring period, when the human organism has a special
need for vitamins; too low temperatures cause irreversible biochemical processes in fruits.
Therefore, it is necessary to use advanced methods of storage. One of the promising
methods of storing fresh agricultural produce, which makes it possible to preserve consumer properties for a long period of time is to develop a gas medium, characterized by an increased content of carbon dioxide and a decreased oxygen content.

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This method is widely used abroad. However, construction of such chambers is associated with difficulties of their air-tight sealing, development of special gas mixtures etc.
Development of a modified atmosphere is possible only in storage of fruits and vegetables in polymer films with a given gas, vapour and water permeability by natural accumulation of carbon dioxide and increasing the content of oxygen in respiration of fruits and
vegetables. Harvested fruits and vegetables continue to grow, they absorb oxygen, evolve
carbon dioxide, heat and volatile organic substances. This physiological process of respiration is described in a simplified way by the equation: C6H12O6 + 6O2 = 6CO2 + 6H2O +
674 kcal. However, the respiration process proceeds according to this scheme only if there
is a free access of oxygen, and oxidation proceeds up to the final products. During the storage in a packaging little permeable for air, the access of oxygen to the product is hampered
and oxidation can proceed not to the end, which results in the emergence of visible signs of
the physiological disorder in the metabolism. Therefore, one of the main requirements to
polymer films for storage of fresh agricultural produce is absolute gas permeability.
However, an excessively high gas permeability makes the film little suitable for packaging fruits, because in such films it is impossible to create an atmosphere with an increased
content of CO2 and decreased content of O2. In films with low gas permeability, free oxygen present in the packaging is consumed for respiration over a short period of time, and
the concentration of CO2 may increase up to the limits dangerous for fruits and vegetables
(more than 610%). Therefore, such films are also unsuitable for packaging fruits and vegetables.
Many polymer films possess a sufficient gas permeability, a selectivity of permeability, the extent of which depends not only on the chemical nature of a film, but also on its
thickness, temperature conditions, partial pressure of the gases and other factors. Films
from high-pressure polyethylene (up to 60 m thick) are used in practice; they possess a
certain permeability for CO2 and O2, weak vapour and water permeability and such important properties as high elasticity, strength, chemical inertness, resistance to external factors,
heat sealability etc.
The idea of using film containers with gas-exchange membranes is a further development of the method of storing fruits and vegetables in polymer packagings.
French scientists proposed and realized in practice a method of regulating the composition of the atmosphere in storage of fruits. The method is based on using the selective permeability of silicon elastomer (polysiloxane) for various gases.
The method comprises four steps: storage of fruits using diffusion exchangers, which
are located outside the storage chamber; storage of fruits using diffusion exchangers located
inside the storage chamber using gas-permeable walls from films (for very large premises);
storage of fruits using small storage tanks with windows closed off with a silicon film (soft
containers from polyethylene, of 5001000 kg holding capacity).
One of the technically simplest variants of using the selective permeability of film materials for regulating the gas composition of the atmosphere are soft polyethylene containers.
Fruits are put into storage in these containers in the same way as in common boxes.
Containers are equipped with inserts (windows) from silicon elastomer. The amount of elastomer is the same as in the diffusion exchanger.
After putting boxes with fruits into the container, its top is tightly fastened, after which
the exchange with the outer atmosphere is predominantly through the silicon window.
Diffusion of gases through the window is a function of the partial gas pressure differential on both sides of the membrane, of the type of cloth used in the film and of the thick-

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ness of the coating of the cloth with silicon elastomer.


The choice of siloxane elastomer to be applied on the cloth is determined by the unique
properties of this material: the gas permeability of polydimethylsiloxane (PDMS) is 1520
times as high as that of natural rubber, which has the highest permeability of all-hydrocarbon elastomers.
By their gas solubility, both these rubbers are close, and a higher gas permeability of
PDMS as compared with natural rubber is explained by a considerable increase of the rate
of gas diffusion. This is also confirmed by the fact that the diffusion coefficient is largely
determined by the nature and structure of polymers, whereas the values of the solubility coefficient depend mainly on the nature of diffusing gas or vapour.
Storage of fruits in containers has a number of advantages: there is no need to seal the
premises, and products are stored at a temperature of +2 up to +7C. Therefore, containers
could be used both in artificially refrigerated and noncooled fruit storages. These features
of the container method of storage make it rather promising, in particular, for a broad use
in collective farms and state-owned farms.
The size of containers could be diverse. However, in each case, for a given area of the
membrane, there is a dependence between the weight of stored apples, storage temperature
and a given content of O2 and CO2 in the container. The violation of this dependence can
leads to unfavourable results of storage. Putting fruits for storage should be done as soon
as possible after harvesting.
Successful storage of food products can be ensured only at a correct choice and maintenance of the main factors of storage (temperature, relative humidity, composition of the
atmosphere) not only for fruits of each species and variety, but even for fruits of the same
variety depending on the growth conditions, picking time and duration of storage.
Provision of required temperature and humidity conditions of storage is done rather
successfully by constructing refrigerating chambers. However, even in perfect refrigerating
storage facilities the losses of fruit-and-vegetable produce are considerable, its vendibility
qualities and nutritive value are significantly decreased, all due to premature overripening,
ageing and damage caused by physiological and parasitic diseases.
Creation of a modified gas medium using selectively permeable film materials (SPFM)
deserves special attention, as this method of storage does not require constructing expensive
sealed storage facilities or reconstructing the existing refrigerating chambers. The method
can be also successfully used under conditions of noncooled storages (warehouses, cellars).
Additional expenses for polymer materials are not large and are totally paid off due to the
significant improvement of the quality of fruit-and-vegetable produce and a decrease of natural depletion of weight and losses. The use of this method makes it possible to put the produce for storage in a modified gas medium directly where it is harvested.
A container design has been developed, which enables a secure protection of the membrane from mechanical impacts and its multiple use. The design makes it possible to carry
out tests of storing fresh agricultural raw materials using SPFM and to perform calculations
of the feasibility of this method as compared with the existing method of refrigerator storage
in open standard boxes and containers. When preparing SPFM for applying onto the base
of polymethylsiloxane composition, the so called spread coating method was used.
Package inserts with membranes and filters from SPFM are operated under conditions
of fruit and vegetable storages without the light; the temperature in storages is +2 up to
+7C. If refrigerator chambers are used for storage, the temperature is decreased to 0 to
2C. The further decrease of temperature leads to irreversible cold damage of the fruits
burns, scalds etc. Relative humidity in package inserts is maintained at a high level

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(9599%), which in violations of storage technology leads to the condensation of moisture


on the walls. During the preparation of the membranes, their pasting, as well as in subsequent operation of package inserts, SPFM can be subjected to deformations and mechanical
damage. However, the main requirements to this type of materials is the high level of gas
permeability and the selectivity of permeability with respect to various gases, mainly to oxygen and carbon dioxide.
SPFM are used for long-time storage of fruits and vegetables not independently but as
membranes. The design of vegetable and fruit containers can be different, which depends
on the kind of produce, charge volume and other factors, but they are fabricated mainly from
a food-grade polyethylene film 80200 m thick.
When fabricating package inserts with membranes, and subsequently gas-selective
heat diffusion devices (CSHD) the main problem was to join the gas-selective membrane
with polyethylene and polystyrene, because these materials are of different chemical nature.
Bonding of the membrane to polyethylene was done by two techniques pasting and
heat sealing; bonding to polystyrene was performed by pasting using intermediate materials. As polyethylene packages with membranes are operated under conditions of high relative humidity (9599%) and even of moisture condensation of the walls of the container,
studies were carried out to determine the strength of pasting with adhesive sealant VGO-1
after holding the specimens in water. A prolonged holding in water proved not to have any
noticeable effect on the strength of pasting.
The second technique suitable for bonding a membrane from SPFM to polyethylene
is heat sealing, which consists of the following. A membrane with round holes 35 mm in
diameter along the perimeter with 5-mm spaces between the holes is put onto a polyethylene
package insert with a window in it. A polyethylene-film covering also with a window in it
is put on top of the membrane. They are pressed by a plate heated up to a temperature of
about 130C. Under the action of temperature and pressure, the fused polyethylene of the
covering is sealed through the holes to the material of the insert. The covering is slightly
larger than the membrane, owing to which the material of the membrane is sealed to the
polyethylene package.
The heat sealing method requires less hand labour as compared with the pasting method. Almost all operations can be mechanized. Besides, raw stuff and materials are saved
there are no expenses for undercollar cloth and adhesive sealant; additional expenses for
polyethylene coverings are insignificant.
Initially, tests of storage of fruit-and-vegetable produce were carried out using containers and package inserts with membranes fixed by the above methods. The design of the
package inserts is such that the membrane was located in one of the side walls of a container.
However, the use of such packages on a commercial scale is difficult due to the complexity of their fabrication, difficulty of using mechanized automated lines.
Poor removal of biological heat of the respiration of fruit-and-vegetable produce in
large-volume containers (300-100 kg) leads to the increase of the temperature gradient in
the bulk of the produce.
All these necessitated a further improvement of the method. However, for storage of
small batches of fresh agricultural produce, as well as for special purposes, e.g., for equipping deepwater ships, expeditions, the method of storage in small packages with membranes remains acceptable.
Placement of a gas-selective membrane in the inner cavity of the device made it possible to protect it reliably from mechanical damage and ensure its multiple use. The design
of GSD enabled introduction of the membrane directly into the bulk of stored produce.

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The method of creating a modified gas medium by means of gas-selective devices using a hose polyethylene film is economical, simple and accessible for practical use in nonhermetic storages of all types.
A gas-selective device has the shape of a funnel with shanks and blades, whose inner
cavity has gas-selective elements. The body of the device was fabricated from a food-grade
shock-proof polystyrene sheet 2.53 mm thick by the method of vacuum molding or pressure casting from granulated polystyrene. The gas-exchange section of the device is perforated.
The device is universal and can be used with hose polyethylene film in all kinds of fruit
and vegetable containers manufactured by domestic industry.
During the storage, it is necessary to check daily the temperature regime in the storage
facilities and to sample and analyze the gases in sampled packages in two days for the first
six days and then once a month. Such kinds of produce as garlic, bulb onion and carrot are
stored at a temperature of 01C, and other kinds of produce, at 34C. At a stabilized regime of the atmosphere in a packaging with produce in the visually normal state, the duration of storage is determined by the necessity related to the produce sales time. The
maximum storage time is 79 months. Storage can be terminated in the case of deterioration of the quality of fruits, as well as at a decrease of the oxygen content below 2% or at
an increase of the carbon dioxide content above 67%.
Activated charcoal absorbs ethers evolved in respiration of fruits, aldehydes and acids,
the formation of which is associated with the disturbance of their metabolism, the biochemical and mechanical injuries of tissues, and ethylene which causes accelerated ripening of
fruits. In storage, fruits are subjected to microbial spoilage, one of the major means of controlling which is to use substances suppressing the development of microorganisms.
Gathering the harvest into
polymer containers with GSHD

Stockpiling

Modular storage

Sales of produce

Sorbic acid is the most efficient of acid antiseptics; it is absolutely tasteless and has no
smell. Its salts (e.g., potassium or sodium sorbate) as aqueous or aqueous-alcoholic solutions are as efficient. Introduction of activated charcoal and any antimicrobial preparation
into the packaging makes it possible to remove excess ethylene and volatiles evolved by
fruits, and also to inhibit the processes of microbial spoilage. For this purpose, a porous hydrophilic material treated with a suspension of the antiseptic and activated charcoal is
placed at the point of fixation of the membrane, as the most suitable place; it is placed from
the inner side of the membrane facing the fruits. Papers of sufficient strength, e.g., kraft,
cloth, paperboard etc. can be used as a hydrophilic porous material. The suspension can be
applied by spraying, immersion or passing between rolls. When carrying out the works, cotton calico impregnated by immersion into a suspension of activated charcoal and sorbic acid
in acetone was used as a porous hydrophilic material. After drying, a gasket was cut from
this material. The size of the gasket was equal to the size of the gas-selective membrane
used. The gasket was placed from the inner side of the membrane. In the case of using the

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gas-selective device for storage, the gasket was placed between the membrane and perforated wall of the GSD. The gasket was fixed the way the membrane was fixed, by adhesive
sealant VGO-1. Storage was performed in unsealed facilities at a temperature of 13C.
Analyses established the food components of fruits to be better preserved in storage in
a modified atmosphere than in a common atmosphere. Noticeable changes were observed
to occur in the content of total sugar, pectins and tannins. The development of an anaerobic
exchange is indicated by the amount of alcohol and acetaldehyde. Under conditions of a
modified atmosphere, accumulation of alcohol and acetaldehyde was observed to be insignificant, owing to which apples stored under these conditions had no physiological diseases.
The economic effect of storing apples in containers with GSD is due not only to the lower
expenses for storage, but mainly due to the increased vendibility of apples.
The recommendation to store food products of only good quality refers not exceptionally to the storage of fruits and vegetables. It is equally valid with respect to other products:
meat, dairy, fish etc.
The meat of a just-killed animal usually has a glossy surface, dark red colour and rubberlike consistency.
After cooking, green meat is usually coarse and is difficult to chew. The smell of such
a meat is weakly expressed due to the absence of aromatic substances. Usually, this meat
is said to be tasteless. Therefore, fresh meat should be subjected to maturation, during which
it becomes tender, juicy and aromatic. Herewith, under the action of enzymes there occur
autolysis, degradation of proteins to polypeptides and amino acids, and breakdown of the
carbohydrate system of the muscle tissue to simpler substances. This leads to the accumulation of lactic and phosphoric acids in the musculature and a shift of the reaction of the
medium to the acidic side. The pH values of the meat vary between 5.6 and 6.0. Part of tightly bound water passes to loosely bound water. Only after biochemical changes in maturation, meat acquires a tender consistency, becomes juicy, and has an expressed aroma and
taste.
The maturation time depends on the quality, integrity and assumed use of meat. The
course of the maturation process also depends on temperature, kind of animal, its age, sex,
on management and feeding conditions prior to slaughtering and its condition during the
slaughtering.
At present, carcasses, half-carcasses or quarters are first cooled for 2448 h at a temperature of 0C and relative humidity of 8590% and air conditioning. At a low air velocity, the temperature inside the meat should be from + to +2C. Herewith, a dried up layer
is formed on the surface of meat. After that, the carcasses are hung up and held in a refrigerator approximately at a temperature of +2C and 85% relative humidity. Air velocity
should be such that to prevent unnecessary losses of mass at these temperature and humidity
regimes. At a higher temperature, meat becomes more tender and matures faster. During
the maturation, it is necessary to observe hygienic conditions and, as far as possible, to
avoid temperature variations of more than 1C.
Under the above described conditions, beef matures in 814 days; pork, about 3 days;
veal and mutton, 37 days.
Losses of mass in maturation of meat according to the described method are rather significant. They differ depending on the species of animal, its age and the properties of meat,
and make 2.55% on average. Dressing losses owing to the removal of dried and
dark-brown parts of carcass surface (facings) are to be added to losses of mass after maturaion. The dressing losses are, as a rule, 1.52%. Thus, the total losses reach 47%, and
in hanging of individual slabs of meat, even 12%.

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After maturation, meat should be consumed as soon as possible; otherwise, it is difficult to prevent further losses.Veal and pork do not withstand a long-time storage at the given
temperature regimes. The storage time of meat at a temperature of 0 up to 2C in a refrigerator can be increased significantly owing to the introduction of 1015% carbon dioxide.
The above described method of preserving the quality of meat by its hanging and cooling is widely used, e.g., in Germany.
In Germany, a special composition was developed, which makes it possible to preserve
meat fresh for five days even at a temperature of 35C. According to the proposed method,
a freshly slaughtered carcass is immersed for 10 sec into a solution of maize starch, cooking
salt, sugar and fruit acid. Experimental checks found this composition to prevent the activity
of salmonella, which cause food poisoning.
For more long-time preservation of the quality of meat, it is kept in frozen state. Deep
freezing is considered to be the best method of meat preservation. Freezing at a temperature
of 40C and strong air motion with high humidity, followed by storage at 18C in the
dark guarantees the preservation of the quality of cattle meat for 1012 and of pork for 46
months; when stored in the dark at 30C, cattle meat is preserved for 2224 months; and
pork, 1315 months without the change of quality. During the storage in a frozen form, the
losses of vitamins, especially vitamin B, are slowed down.
If unpackaged meat is stored in the frozen form, then in storage from 18 up to 20C,
relative humidity of about 90% and good air conditioning, the losses of mass of meat are
considerable.
In freezing, the losses of mass of cattle meat are from 1 up to 2%; and of pork, from 1
up to 1.6%. The losses of mass after 3 months of storage in the frozen form reach, as a rule,
2.23.2% in cattle meat, and in pork, 1.52.0%. The losses strongly vary and depend first
of all on the kind of meat, as well as on temperature and duration of freezing. During the
freezing in a frozen form, meat not only loses its mass but is subjected to other changes,
including the denaturation of proteins and oxidation of fats. These processes also depend
on temperature and time, as well as, in this case, on the action of light; herewith, the
short-range region of the spectrum is especially efficient. The freezing conditions are also
significant for the above processes. In deep freezing, the changes of products are little tangible, because a thin structure of crystals is formed, and, owing to their small growth rate,
a smaller amount of water contained in the cells passes into the intercellular space. At
non-deep freezing, water contained mainly in the intercellular space freezes. Herewith, a
small amount of large crystals is formed, which grow at a large rate, and the muscle tissue
loses much water, and connective tissue is broken. The longer the freezing process is, the
more time it takes for water to diffuse from the muscle fibres or cell protoplasm owing to
the osmosis. The protein being in solution gets denatured owing to a change of the concentration. Water permeability of the cell wall changes. These changes are largely irreversible,
and in the subsequent thawing the meat looses a large amount of cell sap, which contains
nutritive and flavouring substances.
Freezing of meat by liquid nitrogen (196C) is the fastest method of freezing, which
finds an ever wider application in Western practice. Due to evaporation of liquid nitrogen,
this type of freezing prevents the structural changes better, as the result of which the freshness and flavour of meat are preserved till thawing even after long-term storage. Colourless,
tasteless nitrogen changes neither the smell nor the taste nor the colour of meat. It does not
enter into chemical interaction with the product. Owing to an extremely large temperature
difference, the freezing lasts only several minutes.
Technically developed countries use the newest achievements in meat industry and

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avoid losses of mass by means of storing and freezing meat in polymer films. The basic requirements are reduced to the above mentioned sanitary-hygienic norms, which should be
observed in storage of meat.
Besides banning polymer films, from which ingredients of the polymer composition
can migrate into meat, a number of requirements are imposed upon films. They should possess the following properties: protect meat from harmful external effects; not to change the
taste and smell of meat; prevent the loss of flavour; possess a high mechanical strength, as
well as the capability of non-penetration of microorganisms; not to lose the operating properties with temperature changes; possess the required water and vapour permeability and
have the given values of gas impermeability and fat resistance; possess a flexibility and acquire the shape of the packaged product; packaging into the film should be easy and economical not only manually, but also in automatic machines; films should be transparent and
easily printable. Besides, they should be sufficiently cheap so that the economy from reducing the losses exceeds the packaging costs.
The main requirements of foodstuffs hygiene, as well as the technical requirements are
satisfied with respect to polystyrene films, combined polyesterpolyethylene films, as well
as certain polyamidepolyethylene combined films and other films.
Polyester films have a number of advantages. Their mechanical strength is so high that
a thin film can not be torn by hand. Polyester films can be used for fabricating vacuum packagings. They preserve their operating characteristics within admissible limits in the temperature range from 200C up to +255C. This means that foodstuffs packaged into polyester
films can be sterilized by boiling in water or by steam heated up to 120C. Products packaged into polyester films can be scalded, boiled, steamed, stewed, grilled, dried. Along with
this, these films can be used in freezing products by liquid nitrogen down to a temperature
of 196C. As polyester films possess a certain rigidity, air bubbles are inevitable in polyester packages. The film should adhere tightly to meat along the entire surface, otherwise
air cavities with a high relative humidity emerge.
Polyester films belong to a few artificial packaging films, which have an insignificant
permeability for carbon dioxide.
Many polymer film materials are characterized by the dependence of gas permeability
on humidity. Thus, the oxygen permeability of combined (polyamide/polyethylene) films
with an increased relative humidity increases. The oxygen permeability of polyester films
is absolutely not affected.
Packaging of cattle meat into water-, vapour- and gas-impermeable films for maturation and cold storage has significant advantages. Thus, for instance, the quality of meat can
be preserved especially completely during the storage in a refrigerator if the package is
filled with a gas of a certain composition: a mixture of 8590% nitrogen and 16-10% carbon dioxide. This composition favours the storage of meat at a temperature of 0 to +2C.
Nitrogen serves as an inert gas medium. Carbon dioxide evolved in maturation of meat begins to act, preventing the spoilage at a low temperature and a weak concentration of CO2
only in several weeks.
A favourable effect of carbon dioxide is based on the inhibition of the development of
microorganisms. A possible change of coloration due to the microbial metabolism is slower
in this case.
The concentration of carbon dioxide greater than 1015% is undesirable, because the
further increase of the concentration is accompanied by an increase of CO2 diffusion
through the packaging film, owing to which only a limited part of carbon dioxide will be
absorbed by meat fluid.

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Application of polyethylene terephthalate (polyester) films for meat packaging makes


it possible to avoid the use of nitrogen. Meat can be separated from bones and cut into slabs
from a quarter carcass of a temperature plus 12C and pH 6.2 immediately after cooling.
This should be done if possible in 24 days after slaughtering.
Meat of only good quality should be used for storage in films.
Cutting and packaging should be performed in facilities with a temperature of plus
812C for 2040 min. Therefore, it is important that prepackaging and packaging premises be near refrigerators.
Meat of 3 up to 10 kg weight can be packaged into polyester thermosetting packages,
as well as packages from combined films, one of the layers of which is a polyester film.
Thermosetting films are those that shrink at a short heating up to a temperature of plus
685C.
Films acquire this property as the result of a preliminary biaxial stretching. After the
action of the deforming force is removed, the resultant structure of the films becomes unstable. Transition to the stable structure after the external mechanical action is removed can
be delayed either by keeping the film frozen under the operating conditions, so that it is
in a glass-transition state, or else the structure of the film formed in the process of orientation is fixed by rare crosslinks, which link the chain macromolecules into a three-dimensional network. If this system is warmed up, the rare crosslinks would not withstand the
tendency of breaking down the segments of chain macromolecules under the action of the
heat development of microorganisms on the surface of meat. Simultaneously, the danger of
deterioration of the quality of meat (appearance, smell and taste) is decreased. Application
of absorbing pads contributes to the increase of storage time and improvement of the quality
of meat.
Herewith, it should be taken into account that, with a pad for absorbing meat fluid, the
loss of mass is approximately 0.8%. Addition of absorbing material should correspond to
the expected loss.
Packaging into films is also recommended for storing frozen meat. This prevents its
loss of mass, change of coloration etc. In this case, its aroma, vitamins and nutritive value
are preserved. In impermeable films, packaged slabs of frozen meat preserve their useful
properties longer. While packaging into dense films is acceptable for maturation and refrigerated storage of only cattle meat and, on a limited scale, of veal, packaging of frozen meat
into impermeable films is suitable for all kinds of meat. For meat to be well preserved in a
packaging, its quality should be perfect. Meat should be packaged into a proper film with
all rules observed, quickly frozen and properly stored (23 weeks at 02C, maturation and
storage).
Meat of cattle should be matured prior to freezing; the maturation process is almost
stopped by freezing, and thawed meat matures worse due to the known structural and biochemical changes. At room temperature, such meat remains hard for a long time. Good maturation before freezing is required, first and foremost, for slabs of meat intended for
cooking.
Packaging of meat in water-, vapour- and gas-impermeable packages from polyester
films or from polyester combined films for maturation, as well as for storage in frozen condition is an especially effective technique for preserving the nutrients and reducing the losses. Meat matured and stored in packages, as compared with that matured and stored without
packaging, has the following advantages: it is protected from contamination and microbes,
drying, oxidation, discoloration, loss of aroma. Besides, its storage time and quality increase. Such a meat has a greater nutritive value, it is more succulent and tender, and has a

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better aroma. Storage of packaged meat allows a stronger circulation of air in the refrigerator.
Losses of mass in maturation and storage of meat in a refrigerator are restricted to exudation and make 12.5% on average, whereas in usual maturation and storage without a
film they reach 47%.
Due to the use of respective film packages, losses in maturation and storage of meat
can be decreased by two thirds on average with simultaneously better maturation and increased storage time. Meat in impermeable film packages shows no considerable losses of
mass not only during the freezing, but also in storage.
Dressing of carcasses, as well as cutting of meat and its processes can be more rational
and with a relatively smaller labour input.
Storage and transportation of packaged meat in stacked boxes or dispatch in cases increase the labour productivity, make it possible to use the premises more rationally and increase the load-carrying capacity of vehicles by almost 22%.
Packaging of frozen meat into vacuumed packages enables hygienic lossless thawing
in a bath with cold water, which is economic from the point of view of time and energy expenses.
Based on modern achievements of polymer chemistry, synthetic films and materials
on their basis have been created, the use of which for protection of meat and meat products
from spoilage in combination with artificial cold make it possible to significantly reduce
normal wastage and ensure the sanitary well-being of a product.
Fabrication of meat and meat products in a packaged form contributes to the solution
of an important social problem economy of socially useful labour during the sale and consumption of prepackaged products on the market, in catering trade and in housekeeping.
Unfreezing of products in microwave ovens takes only several minutes, so meals should be
prepared in such ovens in packages from polyester films of the type of SP-2.
When using polymer packagings for meat and meat products, the effect of external factors vacuum or modified atmosphere with a low content of oxygen in the packaging on
the complex multicomponent biological system can vary depending on its state, which is
determined by the character of the physicochemical and biochemical processes in muscle
and fatty tissue.
The need to solve the problem of increasing the duration of refrigerator storage of
chilled meat invariably increases as the technological processes of meat production are improved.
Apart from the general increase of meat production, volumes of stored meat in chilled
state increase, the assortment of semifinished meat and meat products becomes broader.
Storage in chilled state using film materials makes it possible to preserve the food nutritive value of products, to decrease losses of mass, to improve the sanitary state of products
and sites of their production, storage and sale.
At present, great attention is paid to novel methods of storing chilled meat, which are
based on vacuumizing and use of modified atmosphere. This required the development of
novel film materials, which possess an increased gas, vapour and moisture permeability;
special equipment and qualified personnel.
From the practice of storing fresh agricultural raw materials and ripening of cheeses,
it is known that the gas composition inside polymer packagings can be modified using film
materials, which possess a selective permeability for carbon dioxide, oxygen, nitrogen and
other gases.
Selectively permeable film materials (SPFM) are used as membrane inserts of soft

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polymer containers.
Changes of the gas composition in packages occur in accordance with the generally
known gas diffusion law, whose driving power is the difference of partial pressures of the
gases on both sides of the material. Owing to this, gas is transferred from the zone with a
high partial pressure to that with a lower partial pressure up to a point of a certain equilibrium.
The rate of the onset of an equilibrium state of the gas phase inside a packaging depends on the selectivity of material of the insert; the rate is assessed by the ratio of the
amount of one gas to that of the other, which pass per unit of time through a unit of 1 atm.
Thus, prerequisites are established for studying the possibility of using gas selective
materials for storage and transportation of chilled meat.
Some of the products, for instance, dry kissels, concentrates of first and second courses, desserts, dry beverages (coffee, cocoa, etc.), freeze-dried food products, etc. readily absorb moisture. Even small amounts of moisture, oxygen and light cause spoilage of
freeze-dried products, instant coffee, babys formulas. These products are well preserved
in vapour-, gas- and light-impermeable packaging, best of all, under conditions of deep vacuum or in an inert gas atmosphere. Dry food products may disturb the integrity of a packaging. Therefore, the requirements to their strength characteristics should be more stringent.
Thus, during the packaging of cereal concentrates into lacquered cellophane the layer of lacquer is damaged by particles of a cereal.
In vacuum packaging, the mechanical impact of a dry product on the material is noticeably increased, which leads to the necessity of using multilayer films based on polyethylene terephthalate. Modern weighing-and-packaging machines exert a considerable
mechanical impact on polymer film materials. This equipment is intended to be used at high
speeds (their performance often exceeds 100 packagings per minute). Packaging material
for this equipment should be strong, have a smooth surface and low friction coefficient. In
most cases, the use of soft, low-strength polymer film materials is inadmissible on modern
weighing-and-packaging equipment. Materials should be sufficiently strong, such as combined materials from paper, aluminium foil, cellophane, polypropylene, polyethylene
terephthalate etc. In a number of cases, e.g., in packaging cloves, cinnamon, coriander, laurel leaf powder, food concentrates, instant coffee etc., a high air tightness is required. Attention should be paid to the fact that a high initial humidity of a product at its airtight
packaging leads to the condensation of moisture on the inner side of the packaging and the
development of mold. Therefore, before packaging, one should be sure that the concentrates
are sterile or else to add a preservative. Thus, it is recommended to add about 0.02% of sorbic acid to kissel concentrates. The maximum admissible moisture content for instant coffee
is 67%.
Packaging of food concentrates into paper or cellophane with a polyethylene coating
enables increasing their shelf lives 1.5-fold, and packaging into combined materials based
on aluminium foil, more than 2-fold as compared with packaging into parchment or imitation parchment paper. The shelf lives of some milk concentrates, such as coffee with milk,
cocoa with milk, cocoa with cream, coffee with cream and scalded cream in paper or cellophane with a polyethylene coating increase twofold as compared with those in imitation
parchment or in labelling paper.
At present, products with a high content of fat store well in combined packaging materials based on paper, cellophane, aluminium foil with a grease-resistant coating based on
copolymers of vinyl chloride with vinylidene chloride, ethylene with vinyl acetate. These
coatings are applied as a melt and water emulsions latexes. Fatty products store well in

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

containers from cellulose derivatives ethrols. Food concentrates of the first and second
courses are well stored in combined materials based on aluminium foil. Herewith, it is recommended to add into the fat-containing concentrate of a food product an oxidation-preventing substance, e.g., dodecyl gallate (up to 0.01% of the weight of fat).
Application of paper with a coating from polyethylene (viscotene) or cellophane with
a polyethylene coating (PC-2, PC-3, PC-4) instead of imitation parchment makes it possible
to increase the shelf life of milk concentrates from 34 up to 68 months. For packaging
of dry products from potato, the following are successfully used: for semifinished crackers,
a polyethylene film and paper with the polyethylene coating; for roasted crackers, PC-2
film; for potato crisps, a film from a mixture of different grades of polyethylene, PC-2, etc.
For packaging of dried potato with a moisture content of 68%, four-layer kraft paper bags
with a double polyethylene coating were successfully used. In this packaging, the product
was stored up to 6 months without losing its edibility characteristics. Freeze-dried fruits,
berries, purees and other products store well in glass and tin cans. However, this kind of
containers have drawbacks: they are brittle, unsuitable for transportation (glass containers),
they corrode (tin cans), their weight is large (sometimes exceeding the weight of the contents nine times). Therefore, more advanced containers for these products are made from
polymer films, e.g., lavsanpolyethylene (SP22), films based on aluminium foil plied up
with polypropylene or a mixture of certain brands of polyethylene (steralkon, lamister, folgoplen), polyethylenepaperfoil, etc. Materials based on foil with application of a polyethylene film or SP-2 film possess the best protective properties.
As food products degrade, there occurs decomposition of vitamin C. The better a container is, the slower the decomposition of ascorbic acid proceeds. The efficiency of the protective properties of containers could be judged by the change of coloration of products in
storage, as well as by the change of the composition of aromatic compounds present in the
food product.
Airtight packaging of food concentrates can be done into packages from polymer and
combined materials on packaging lines. For this purpose, both Russian equipment (e.g., of
the type of the KMKh-75 automatic machine) and Western equipment (e.g., of the company
Hassia GmbH) are used.
Granular food products, e.g., corn flakes and dry breakfasts, are packaged into rectangular boxes from chrom-ersatz paperboard (240250 g/m2) with the inner package insert
from thin paper (4070 g/m2) coated with polyethylene. This line is manufactured by the
Swedish company Cristiagren.
The tendency of manufacturing food products both in this country and abroad is that
products of a high degree of preparedness become more widespread. In particular, frozen
ready-prepared meals, semifinished products, fruit-and-vegetable juices, etc., are offered
for sale in increasing amounts. Packaging of food products intended for freezing can be carried out by various methods. Thus, for instance, trays fabricated from an aluminium alloy
with several divisions are used for this purpose. The inner surface of the trays was covered
with a corrosion-resistant lacquer; its upper surface was finished with lacquered aluminium
foil, which was sealed to the lips of the tray. For packaging of frozen products, containers
from polymer materials are used, sometimes in combination with traditional materials. Attempts are made to fabricate containers withholding the sterilization by boiling followed by
warming-up in hot water. Packages from a polyethylene terephthalate film plied with a
polyethylene film are used for this purpose the most. A package fabricated from such a material (e.g., from SP-2 film) is transparent, which makes it possible to see its contents. The
main requirements to the material for packaging frozen ready-prepared meals are as

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95

follows: its use should be permitted by the State Sanitary Inspection for contact with a given
concrete product under concrete conditions of storage, transportation, sale and use; it should
be sufficiently processable and economical, airtight, strong and elastic.
For a material not to become brittle at a deep freezing to minus 5060C or refrigerator
storage at minus 2030C, it should be sufficiently elastic. Besides, packaging material intended for prepackaging frozen ready-to-eat meals should withstand rapid defrostation and
warming-up of the packaged product in boiling water.
As the packaged food product is protected by polymer material, it proves to be possible
to use for its freezing the most progressive method of contact freezing. This method is performed in contact plate freezers or in refrigeration brines. The packaging prevents the product from spoilage by burns. Slowing-down of the chemical reactions at low temperatures
enables the use of polyolefins, such as polyethylene and polypropylene, in contact with fatty
products.
Frozen ready-prepared meals, as a rule, are packaged either into packages from
single-layer or multi-layer polymer materials, or else into boxes of various designs with
thermoplastic coatings.
Type of food product

Dried fruits and vegetables


Corn products (popcorn, cornflakes), oat diet products,
kissels, dried potato puree and
other dry products containing
no fat
Potato fried in oil (chips,
crackers)
Food concentrates (first and
second courses) containing
no more than 1015% fat
Food concentrates containing
more than 15% fat

Milk concentrates (based on


coffee, cocoa)
Instant coffee
Spices and food additives

Recommended kinds of packing materials


Non-long-term storage

Long-term storage,
stringent storage conditions

Polyethylene-coated kraft paper


Polyethylene-coated cellophane
Polyethylene-coated paper and
paperboard
Polyethylene-coated cellophane
Polyethylene film

Polyethylene-coated polyester
(lavsan)
Polyethylene-coated aluminium
foil (lacquered on the outside)

Lacquered cellophane
Fat-resistant copolymer-coated
paper
Polyethylene-coated paper.
Polyethylene-coated cellophane

Lacquered aluminium foil with


fat-resistant copolymer coating

Lacquer aluminium foil,


paper polyethylene
Lacquer paper, aluminium
foil polyethylene
Fat-resistant copolymer-coated Lacquer aluminium foil,
paper and paperboard
paper fat-resistant copolymer
Fat-resistant copolymer-coated coating
cellophane
Lacquer paper, aluminium
foil fat-resistant copolymer
coating
Polyethylene-coated cellophane Cellophane aluminium
foil polyethylene
Cellophane aluminium foil Cellophane aluminium
polyethylene
foil polyethylene
Lacquered cellophane
Cellophane aluminium foil
Polyethylene-coated cellophane polyethylene
Cellophane aluminium
foil copolymer coating
(of the type of CVC)

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

(continued)
Type of food product

Recommended kinds of packing materials


Non-long-term storage

Freeze-dried food products


(humidity 23%)

Polyethylene-coated lavsan
Cellophane aluminium foil
polyethylene

Long-term storage,
stringent storage conditions
Lavsan aluminium foil
polyethylene
Polyethylene lavsan
adhesive lavsan polyethylene; polyethylene lavsan
adhesive fluoroplastic
polyethylene; lavsan aluminium foil polyethylene
aluminium foil polyethylene

Packages from polyethylene terephthalatepolyethylene SP-2 are characterized by the


range of working temperatures from 70 up to +120C. Ready-prepared meals are frozen
at these temperatures at a temperature of minus 6070C, and unfreezing and warming-up
can be performed directly in the package. It takes the customer a minimal time to prepare
the frozen product for consumption. If the frozen product, e.g., the first or second course,
is to be consumed in the hot state, its preparation would take a maximum of 12 min or less
if a microwave oven is used. If the frozen meal is to be consumed in the cold state, e.g., it
is a dessert, then its preparation requires about 1 min. After the preparation, the product can
be put from the package into dinnerware by cutting one of the sides of the package.
Frozen meals can be packaged into films either from high-density polyethylene or
from a mixture of low- and high-density polyethylenes. These films withstand sterilization
in boiling water at 120 and even 130C, they are more transparent and more resistant to fats.
Films from polypropylene are well heat-sealable. Films from polyethylene terephthalate are
characterized by even better protective properties. They withstand the action of low (minus
4460C) temperatures and boiling in water at 130C, are low-permeable for vapours and
gases; are characterized by a good resistance to attrition and impact loads. Their disadvantage is poor heat sealability, which in practice makes impossible the use of these films on
automatic packaging lines. Therefore, the polyethylene terephthalate or, as it is often called,
polyester film is plied with a film from polyethylene or polypropylene. The polyethylene
terephthalate film provides for such properties of the material as strength, resistance to attrition, gas impermeability.
The inner layer from polyethylene or polypropylene ensures the heat sealability of the
material. Its disadvantage is that it is in short supply and expensive.
As we mentioned above, storage of the most biologically active products or in prolonged storage times of food products requires that packaging material has a combination
of high protective properties and light permeability. In these cases, multilayer polymer film
materials are successfully used, one layer in which is aluminium foil.
Such a type of packaging material, e.g., for packaging infants food, was developed at
the Moscow Technological Institute of Meat and Dairy Industry together with workers of
from the Paper-and-Packaging Plant of the Ministry for Meat and Dairy Industry. It was
called folgoplen. Cellophane from an unreeling roll is fed to the plying rolls of a Werner
and Pfleider line. Before the bands of cellophane and aluminium foil are pressed together
by the rolls, a thin layer of polyethylene melt is to be put between them on the cellophane
surface. This thin layer is to paste cellophane and foil together. This operation produces a

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97

three-layer (cellophanelow-density polyethylenefoil) film. This material is made heat


sealable by applying a polyethylene melt on the foil. The layers of polyethylene melt applied from above are not pressed one to another until the polyethylene melt hardens. Therefore, to provide for a sufficiently good adhesion of the layers one to another, the
polyethylene melt is applied at a high temperature of the order of 270C. At this temperature, intensive oxidation of polyethylene is initiated. The active centres formed in polyethylene molecules are capable of interacting with the packaged product, causing undesirable
chemical reactions, which lead to spoilage of the packaged product. An example of these
reactions is the rancidification of fat. To avoid such phenomena, one more layer of polyethylene is applied on the surface of the oxidized polyethylene layer at a temperature sufficient for it to melt but insufficient to be oxidized.
To increase the strength of adhesion at as low temperature as possible, the surface of
films is treated by a corona electric discharge.
Besides folgoplen, other light-impermeable materials with high protective properties
are polyethylenefoilpaperpolyethylene, cellophanefoilpolyethylene and others.
As for boxes from paperboard, chrom-ersatz or dense paper coated with a layer of thermoplastic polymer, the following combinations are the most recognized: the outer layer
paraffinepaperthermoplast; paper can be replaced by chrom-ersatz. The material consisting of paraffinepaperaluminium foilthermoplast is widespread. In all combinations
considered, the inner layer is a thermoplast, which is polyethylene or polyvinyl chloride,
polyisoprene hydrochloride, saran (copolymer of vinyl chloride CH2=CHCl with vinylidene chloride CH2=CCl2), compositions of copolymers with paraffine.
Great importance is attached to the expansion of production of ready-prepared meals,
including frozen stuff. To date, many frozen ready-to-eat meals are manufactured, such as
meat balls in red sauce, stewed beef, beef goulash, minced beefsteak, kidneys in red sauce,
stewed pork. Two portions of these meals are packaged into paperboard boxes 1207050
mm in size. A similar packaging for four portions is also used. In this case, the paperboard
box is 1809050 mm in size. Inside, boxes are layered with lacquered cellophane. The
packaged product is frozen in fast freezers at temperatures of minus 3040C for 23 h.
Within this time, the temperature in the bulk of the product reaches 18C. At approximately this temperature, ready-to-eat meals are stored in refrigeration chambers for up to one
year. Frozen meals are transported at temperatures not higher than 15C. In trading networks, they are stored at a temperature of 18C. In five months of storage at minus
1820C, frozen ready-to-eat meals, packaged into a paperboard box with an insert from
lacquered cellophane and heat sealed, lose from 1 up to 3% of their initial weight.
Frozen fruit juices preserve well their valuable nutritive properties in polymer containers. Being packaged into bags from the polyethylenecellophane film PC-2, frozen fruit
juices preserved their taste, colour, flavour, vitamin content for three years of refrigeration
storage at a temperature of minus 1820C. These results were obtained in storage of frozen
apple, grape, tomato, cherry, black-currant etc. juices. Similar results were obtained in storage of these juices in packages from paper with a polyethylene coating and from multilayer
film material (cellophanealuminium foilpolyethylene).
Commercial production of frozen juices tomato, apple and grape in Tetra Pack
packages was introduced. The packaging material was paper with a polyethylene coating
on one side and with a thin layer of paraffine on the other side. This material was first sterilized by irradiation by a bactericidal lamp, and then was converted into a hose by wrapping
and heat sealing the longitudinal seam. Sterilized fruit juice was fed to the hose thus obtained. The transverse sealable elements form a chain of tetrahedral packages cut from the

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hose. The cut tetrahedra are put into transport containers. After packaging, the juices are
immediately frozen in fast freezers. The freezing takes 3.54 h.
The described freezing method, in contrast with thermal preservation of, e.g., tomato
juice, enables preserving a major part of vitamin C, whereas the microbiological characteristics (bacterial content) in storage of frozen juices at 18C for one year do not change in
practice. Frozen juices are defrosted in the package. If the unfreezing is done in the air, its
duration is 56 h; in flowing water, it lasts 1.01.5 h. Unfrozen (defrosted) juices are stored
in the package in different ways depending on the conditions: at room temperature, no more
than 24 h after defrosting; in a domestic refrigerator, for up to one week; and in refrigeration
cabinets of trading networks (at a temperature of 8C), for up to two months.
Automatic lines similar to those described enable packaging of spreads (jams, creams,
concentrated fruit-and-vegetable juices) also in packages from polymer and combined materials of the type of PC-2. Packages from paper with a polyethylene coating are also used;
sometimes, even simply from polyethylene.
Concentrated and natural juices, sauces, syrups, fluid food concentrates in general are
at present packaged either into paper or paperboard containers with a polymer coating, or
else in bottles or canisters from polymer materials. Fluid preserved products are successfully packaged into rectangular and tetrahedral containers. The prepackaging of natural and
concentrated juices into these containers, which are characterized by a high airtightness, is
similar to that of long-storage milk into tetra packs. Such packaging lines (Tetra Pack Aceptic) were developed by the Swedish company Tetra Pack and found wide use not only for
packaging milk but also for aceptic filling of fruit-and-vegetable juices and other fluid food
products.
A combination of paraffinepaperaluminium foilpolyethylene is used as a material
for packaging fruit-and-vegetable juices. This material is passed as a band through a bath
with a hydrogen-peroxide solution and is used to form a continuous tube with the continuous sealable seam. The inner surface of the tube is warmed up by an infrared source to eliminate the remaining hydrogen peroxide and for additional sterilization. A food product is
fed to the sterilized tube. Naturally, the bottom of the tube is sealed by the transverse seam.
The transverse sealable seams are implemented by means of sealable elements, as the tube
is filled with a food product. The continuous chain of tetrahedra formed in this way is cut
into separate packagings.
The packaging material used for these purposes it consists of the outer layer of paraffine or lacquer, then paper, aluminium foil and the inner layer of polyethylene is characterized by the capability of being heat-sealed and forming airtight packagings. It protects
well the packaged product from microorganisms, light, oxygen, air; and prevents the loss
of moisture. In such a packaging, it is possible to store natural or concentrated
fruit-and-vegetable juice under usual conditions for up to one year.
Polymer materials characterized by a high gas impermeability are also used for storage
of sterilized food products. In this case, the bactericidal action of gaseous chlorine, formaldehyde, propylene oxide, ethylene oxide and other gaseous substances is used. In preservation of food products in polymer packagings, it is natural to use only hygienically
harmless gaseous ethylene oxide and propylene oxide, as well as a mixture consisting of
60% ethylene oxide and 40% carbon dioxide. Under usual conditions, inhibition of the microflora in such a gas mixture takes 46 h. To provide for the safety (to exclude the possibility of explosion), mixtures of ethylene oxide or propylene oxide (no more than 17%) with
such inert gases as nitrogen, carbon dioxide, freon, etc. are used. The process is accelerated
by increasing the pressure of the gases up to 68 kgf/cm2. The thickness of the walls of the

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polymer packaging should not exceed 60 m.


Sterilization of food products by gaseous substances can be done not necessarily in
polymer packagings with good gas permeability. If a product is packaged in an airtight
package from polymer material with low gas permeability, the polymer package is vacuumized, filled with a bactericidal mixture of gases and sealed. In this case, the materials
used are based on foil, such as cellophanealuminium foilpolyethylene,
cellophanepolyethylene. The absence up to the present of domestic packaging materials
of the type of lavsanfoilpolyethylene mixtures, lavsanpolyethylene, etc. is due to the
lack of supply of polyethylene terephthalate. Its high cost as compared with cellophane is
compensated by the adaptability of the packaging process and a high quality of the packaging.
The specific properties of these materials are especially pronounced in packaging thermally preserved food products. This preservation can be performed both at 100C and at a
higher temperature. In the former case, the treatment process is called pasteurization; in the
latter, sterilization of the food product. In thermal preservation, the polymer packaging material should be temperature-resistant. At a temperature higher than 100C, an increased
pressure is created inside the packaging, so special attention should be paid to the ability of
the material to form strong seams and to preserve airtightness of the packaging within the
entire range of working temperatures.
In practice, there is no individual polymer film, from which one could fabricate a package suitable for thermal preservation of food products in it. This is due to the fact that, as a
rule, heat-resistant polymer materials poorly yield to heat sealing. Besides, there are a number of other reasons, such as unsatisfactory sanitary-hygienic properties, strong deformation or thermosetting; high gas, vapour and aroma permeability, owing to which polymer
materials are used for the considered method in combination with other polymer materials
or with aluminium foil. In such combinations, high-density polyethylene and its mixtures,
polypropylene, polyamide, polyethylene terephthalate etc. are used for thermal preservation of food products in packages.
The most widespread combinations of individual films in combined film materials for
packages suitable for thermal preservation of food products are as follows.
Polyethylene terephthalatelow-density polyethylene is suitable for thermal preservation at a temperature not higher than 105C and for packaging products containing no
more than 30% fat. If, instead of LDPE, a mixture of low- and high- (or medium-) density
polyethylenes is used, then the combination of polyethylene terephthalate and polyethylene
withstands sterilization at a temperature of 120C. The material described above but reinforced with the central layer of aluminium foil was found to be good in long-time storage
of sterilized products. In the recent decade, the most advanced material for storage of food
products proved to be a combination of polymer lacquerplastic aluminium
foiladhesivepolypropylene. As a rule, this material is used for fabrication of containers/packagings by the deep draw extrusion method. The polypropylene film in particular
cases can be used for sterilization of food products in the heat treatment up to 130C and
as an individual film. However, owing to its high oxygen permeability, the film from
polypropylene can not be used for storage of products sensitive to the action of oxygen, and
such products are numerous.
For sterilization of food products with a high content of fat at a heat treatment up to
130C the French company Organico manufactures a film material from polyamide under
the tradename of Rilsan. For heat treatment of any food products by heating up to 130C,
a film from polytrifluorochloroethylene can be used.

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An example of the thermal preservation of food products in packages from a polymer


material is a method of pasteurization of dried fruits: plums, cherries with increased
moisture content of up to 30%. This method was developed in the Moldavian Research
Institute of Food Industry. Hermetically sealed into packages from polyethylene or
polyethylenecellophane film PC-2, dried fruits (200-gram portions) are passed through a
tunnel convection drier. The total time of holding a package in the drier is 12 h at a temperature, which provides for the warming-up of the product up to 8085C. At this temperature the product is pasteurized, which enables preserving products with up to 30% moisture
for no less than one year.
Above, we have already attracted the readers attention to the fact that in the described
methods of preservation special attention should be paid to the strength of sealed seams and
to the prevention of the loss of airtightness of the packaging owing to the increase of pressure inside the package. Research has shown that the strength of sealed seams should be no
less than 80% of the strength of the base material. The maximal strength of the heat seal is
provided for at its width of 56 mm, and in the case of thermoshrink materials it should be
even smaller. At the width of 120 mm, the strength of the seal seam decreases owing to
the setting of the material and the emergence of internal stresses, which contribute to its
breakdown. To compensate for the pressure emerging inside the package at the thermal sterilization in an autoclave or in a sterilization vessel, a counterpressure is created and maintained. During the sterilization of the products in packages from polymer materials, a
pressure exceeding that emerging inside the package is maintained in the autoclave. Otherwise, packages inflate. As the autoclave begins to be cooled, the heat carrier cools down
quicker than the content of the package. Owing to this, the difference of pressures in the
package and outside it can prove to be larger than the value the package can withstand without breaking down. To avoid the disturbance of airtightness of packages, special attention
should be paid to the maximally possible elimination of air from packages prior to their sealing.
Sterilization studies of such products as tomato pulp and collops in polymer packages
showed an advantage of the steam-air method of thermal sterilization over the water method, because it is easier to maintain the set parameters of the process in the former case. The
external pressure in the course of the process should be 0.20.3 atm higher than the internal
pressure. At a temperature of 100C, the counterpressure should be of the order of 1.251.3
atm. At a higher temperature, excess pressure is increased by 0.3 atm for each 5C. In sterilization by this method at 100C of fruit juices, at 117C of liver sausage and at 121C of
green beans and soup from champignons, the best results were obtained for films from
polypropylene and polyamide. The sterilization process took 1530 min. The quality of the
products was preserved for 6 months. Until now, heat treatment of food products in packages from polymer materials has been considered. However, thermal preservation of food
products in polymer containers can also be successful.
Herewith, thermal preservation of such fruit-and-vegetable products as juices, compots, confiture, jam can be done at a temperature not higher than 100C. Packaging of these
products into polymer containers is sufficiently easy. In some cases, the product heated up
to the required temperature is poured into containers, and in other cases the packaged product is heated in containers at a temperature of 80100C. The described method of sterilizing food products in polymer containers is characterized by some features. As rigid and
semi-rigid containers are readily deformed both at excess internal and at excess external
pressure, the success of the process depends on the correct choice of the regime of application and removal of the counterpressure.

CHAPTER 2

101

Fabrication of polymer containers is accompanied by the emergence of the so-called


internal stresses. Under the action of these stresses, a nonuniform shrinkage develops during the heating of containers. The shrinkage is avoided by the correct choice of the regimes
of application and extent of counterpressure. This choice is required in transition from one
type of polymer containers to another, as well as in changing the sterilization regime. The
use of vacuumizing of the packaging should be specially accounted for. Shrinkage and the
related change of shape of the polymer containers are eliminated by warming the containers
before filling them. Thus, for instance, cups from high-density polyethylene or from
polypropylene should be warmed before filling for 30 min at a temperature 510C higher
than the sterilization temperature, i.e., for HDPE at 110C and for polypropylene at 130C.
The sterilization regime in such cups is characterized by a maximal temperature of
120125C.
Rigid polymer containers are closed either by metal or polymer lids. When using metal
lids, the sealing of polymer containers is done by mechanical methods similar to those used
in the case of tin or glass containers. These methods include vacuumizing. When using
polymer lids, the sealing is done by heating, and vacuum is created either by special means
or due to a decrease of volume of the product during its cooling. In sterilization of food
products in polymer packages with metal lids, it is recommended to use the following values of counterpressure: at the sterilization temperature of 105C, counterpressure of 0.7
atm; at 112113C, 0.8 atm; at 116117C, 0.9 atm; at 129C, 1.0 atm.
In the recent decade, another widespread method of sterilizing food products has been
sterilization by radiation. This method imposes special requirements on polymer materials,
such as resistance to ionizing radiation within the limits of the doses used in preservation;
absence of harmful substances emerging in this method of sterilization; absence of foreign
taste and smell. Tests have shown that in sterilization of food products by gamma rays from
a cobalt source at doses common for preservation of food products (0.55.0 Mrad), the major characteristics of a number of polymer materials do not undergo noticeable changes.
Such materials include, for instance, films from polyethylene, polypropylene, polyamide,
polyethylene terephthalate. The characteristics of strength, gas and vapour permeability,
as well as specific characteristics mentioned above remain within the normal limits. Such
films as from polyvinyl chloride, from copolymers of vinyl chloride with vinylidene chloride, from polyisoprene hydrochloride have a foreign smell when irradiated even by the doses of 0.10.2 Mrad. The most resistant to radiation sterilization of food products are
considered to be cellophane lacquered with nitrocellulose lacquer, nonlacquered cellophane, polyethylene terephthalate and polyamide films.
At the radiation impact on multilayer polymer and combined materials, the endurance
of the least-resistant components increased about 1.5-fold. A foreign smell emerging in irradiation of polyethylene is due to the evolution of gaseous products: carbon dioxide, hydrogen, ethylene, propane, butane. In irradiation of polyethylene terephthalate, the evolved
gases were carbon dioxide, nitrogen, oxygen, water vapours and other volatiles. Irradiation
of films from copolymer of vinyl chloride and vinylidene chloride yielded a number of gaseous products with a sharp smell: chlorine, hydrogen chloride, hydrocarbons and some carcinogenic products.
In domestic practice, good results were obtained in radiation preservation of a number
of fresh fruits and vegetables, raw meat, meat culinary products, poultry and other food
products in polymer packagings. As a rule, products were subjected to small radiation doses
(0.51.2 Mrad). The most promising in this respect proved to be films of the type of PC,
paper with a polyethylene coating, polyethylene terephthalate films. In this case we mean

102

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

domestic polymer materials, to which we should also add lacquered cellophane suitable for
this kind of sterilization of products not containing a large amount of moisture. Polyamide
films of the type of rilsan and nylon showed good characteristics. Of special interest are the
results of radiation treatment (0.6 Mrad) of beef meat packaged into cellophane with a polyethylene coating. Meat treated in this way had no foreign smell and stored well under room
conditions for up to two weeks. Pork at the same method of preservation stored for up to
three weeks. Hens and ducks, at a slightly large irradiation dose (1.0 Mrad), stored under
room conditions for up to one month. Meat culinary products irradiated with 0.8 Mrad
stored in this packaging for up to four months.
The described method of storage is also applicable for fish and fish products. Irradiation by a dose of 1.0 Mrad at a temperature of 05C made it possible to store unfrozen
herring for 60 days, fresh pike for 60 days, unfrozen cod for 120 days, fried fish for 60 days,
fish in tomato sauce and in vegetable marinade for 365 days.
With the rise of production and due to the appearance of polymer materials exceeding
the traditional materials (wood, tin, cardboard, paper, glass, natural cotton fibres, tarpaulins
etc.) fish industry came across the problem of using these advanced materials as packaging
and containers for transportation and storage of fish products; consumer containers for
packaging and sales of various fish products, including culinary products.
To provide for the introduction of new materials in fish industry, R&D and process
design units were organized to carry out work in the following directions:
research into polymer materials satisfying the physicomechanical and sanitaryhygienic requirements to packagings and containers for fish products and to synthetic fibres
for fishing nets and tackles
development of polymer containers designs
mechanization of prepackaging/packaging of fish products into polymer containers
R&D works for the organization of enterprises and plants for production of polymer
containers.
These measures made it possible to organize production of polyethylene boxes of
1025 litres in capacity; polyethylene barrels of 50 litres in capacity; small packages with
overprinting; inserts, bags and packages for whale meat, salt fish, frozen fish; 1.5-litre polyethylene cans with overprinting; polyethylene cans of 0.10.4 litres; trays from polyvinyl
chloride.
Production of goods in small packages was increased. For processing of marketable
fish products, new fish-processing complexes were put into operation for production of fish
delicacies in places of consumption.
For packaging of products into consumer containers, use is made of polymer films,
cartons and combined materials based on paperboard, paper, foil with a polymer coating.
The use of polymer materials for packaging, transportation and storage of fish products
makes it possible to free traditional materials woods, white tin, aluminium, glass, etc. This
decreases the costs and consumption of materials in production of containers/packagings.
For instance, production of a 50-litre barrel from polyethylene for packaging cod liver oil
requires three times as less materials as compared with 10-litre glass flasks.
New combined packaging materials used in fish industry are aluminium foil polypropylene (of the type of steralkon) and aluminium foil coated with heat sealable lacquers.
The steralkon packaging is strong, light, glossy; makes it possible to produce solid-drawn
cans of various configurations, which possess airtightness and enable sterilization of the

CHAPTER 2

103

product. There are several lines manufacturing these cans for fish industry.
Domestic industry assimilated the filling and closing equipment operated on polyvinyl
chloride and polystyrene (cases of packagings) and aluminium foil with heat sealable
lacquer (lids of packagings).

104

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

3
3.1

Combined Packaging
Materials Using Cellulose
and Its Derivatives

Internal stresses in coatings using cellulose

Polymer coatings find wide use for protection and decorative finishing of traditional materials (metal, woods, glass, paper, etc.), as well as in the development of plied and combined
materials of various purposes.
In developing the physicochemical bases for production of these materials, of great importance is to study the effect of structural transformations on the properties of polymer systems in their transition from the liquid to the solid state. A peculiar feature of this transition
for polymer coatings is that their formation mechanism passes the stage of gelation and is
accompanied with a sharp inhibition of relaxation processes, which lead to the emergence
of internal stresses (BH).
Studies of the durability of polymer coatings have established that their service life is
largely determined by BH, capable of inducing the spontaneous exfoliation and decomposition of polymer coatings on rigid and elastic supports. Therefore, of great scientific and
applied importance is to develop the physicochemical ways of decreasing BH. This problem is topical in developing packaging materials for food products, as they affect the protective properties of packagings.
Usually, low-molecular-mass plasticizers are used for this purpose. Their mechanism
of action is related to the weakening of intermolecular interaction between structural elements and to the increase of their mobility, which leads to the relaxation of stresses. This
effect is also achieved in the formation of polymer coatings under more mild conditions,
e.g., at (relatively) low temperatures. However, the use of these regularities for monitoring
structure formation in polymer systems is not always efficient, as, along with the decrease
of BH, the physicomechanical, adhesion, thermophysical, dielectric and other properties
are considerably worsened in this case.
In this connection, it is important to decrease BH not during the weakening but during
the intensification of intermolecular interaction between the structural elements. This
would also make possible a considerable improvement of the performance properties. This
effect is achieved by forming a three-dimensional network from supramolecular components available in the liquid system before the onset of its solidification due to the emergence of local bonds, whose strength is commensurable with the energy of thermal motion.
The appropriateness of forming such a network ensues from the new views of the mechanism of BH in polymer systems. The regularities establishing the interaction between the

106

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

character of structural transformations in liquid systems and the incompleteness of relaxation processes were the basis for developing new physicochemical views of the ways to
decrease BH in polymer coatings, based on the development of an ordered thixotropic
structure in film formers and fixing it in ready-prepared products. This is the essence of the
phenomenon of a decrease of BH.
Thixotropy is one of the forms of gelation: such a gel is transformed into a fluid at a
weak mechanical impact, e.g., in mixing, and in a quiescent state a network again emerges
in the fluid; the peculiar feature of the network is that overstresses in it rapidly relax, which
enables formation of products with higher performance characteristics. The effect of a thixotropic decrease of BH is universal and is observed during the formation of polymer coatings, adhesive layers, filled and reinforced systems from monomer and oligomer
compositions, solutions and dispersions of polymers of different chemical composition.
However, not all polymers are readily transformed into thixotropic gels, so new
methods of creating them in various film-forming systems were developed. This is achieved
by introducing special additives to liquid systems. In some cases, these are oligomers forming bridges between supramolecular structures; in other cases, polymers creating a threedimensional network in monomers, oligomers, dispersions and solutions of polymers.
For polymer dispersions with large particles, universal modifiers are efficient: first
they break particles into more fine structural elements, and then crosslink them into a
three-dimensional network. The role of these modifiers can be played by monomers and oligomers, polymer electrolytes adsorbed by particles of dispersions, surfactants.
The gel formation mechanism was studied by various physicochemical methods:
infrared spectroscopy, high-resolution nuclear magnetic resonance, electron paramagnetic
resonance, scanning and transmission electron microscopy; rheological, thermophysical,
physicomechanical etc. methods.
The phenomenon of a thixotropic decrease of BH does not depend on the method by
which the thixotropic structure is created; it can be produced as the result of adding poor
solvents, branched oligomers, crosslinking agents, structuring systems, surfactants, dispersants.
In many cases, it is much more convenient to work with thixotropic systems than with
liquid or solid systems. They are processable, impregnate fibrous materials less and do not
bleed on paper, which is important in printing production and other industries.
The development of a thixotropic structure makes it possible not only to considerably
improve the performance characteristics of polymer coatings. In a number of cases, it enables the complete exclusion of low-molecular-mass plasticizers (readily dropping out in
the process of ageing and, thus, sharply decreasing the durability of the coating) from the
formulation of rigid-chain polymers. The authors used the phenomenon of a thixotropic decrease of BH to develop elastic polymer coatings based on nitrocellulose (NC) with high
physicomechanical properties. Usually, plasticizers are used for this purpose in polymer
coatings from NC, in particular, castor oil, which is in short supply, at a 1:1 ratio. Grafting
of other polymers to NC does not exclude plasticizers, either. NC was modified by polyurethane oligomers with a 0.30.5 ratio of the isocyanate and hydroxyl groups. The extent
of oligomer branching was regulated by introduction of different amounts of triol. Figure
3.1 presents the kinetics of BH changes during the formation and ageing of polymer coatings. It is seen that significant BH emerge in polymer coatings from nonplasticized NC.
Introduction of castor oil at a ratio of 1:1 decreases BH by an order of magnitude. However,
the properties of such polymer coatings are unstable, which is indicated by a sharp increase
of BH during the thermal ageing of polymer coatings. A significant decrease of stresses is

107

in, MPa

CHAPTER 3

1.0

0.6

2
3
4
5

0.2

12
40
Time, h

80

120

Figure 3.1 Kinetics of the buildup of internal stresses during the formation and thermal ageing of
polymer coatings from a 10% solution of NC in butyl acetate: initial (1), plasticized by castor oil (2),
modified by weakly (3), medium (4) and strongly (5) branched oligomer.

observed as a thixotropic structure is created in polymer coatings by means of highly


branched oligomers. Polymer coatings from such systems are distinguished by good physicomechanical properties (see Table 3.1) before and after the ageing.
Table 3.1
Additive

Polyurethane oligomer,
weakly branched

strongly branched

medium branched

Castor oil

NCO/OH

Content of
additive,
weight
fraction

Tensile strength,
MPa

Breaking elongation,
%

before
ageing

after
ageing

before
ageing

after
ageing

0.3
0.5
0.5
0.3
0.4
0.5
0.0
0.1
0.3
0.5
0.7

90
90
110
90
90
90
100
100
100
100
100

24.0
28.1
8.5
28.6
32.4
43.7
0.06
2.0
7.6
8.7
10.0

23.4
28.0
8.8
29.3
31.5
39.2
0.03
3.3
8.3
10.0
15.0

48
80
91
60
60
20
640
247
95
76
48

50
81
96
60
60
22
600
213
88
72
41

90
100
110

16.7
14.7
14.6

13.1
11.8

60
51
68

30
50

Polymer coatings from NC are characterized by an inhomogeneous globular structure.


The globular morphology of the structural elements is preserved in the presence of castor

108

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Figure 3.2 Structure of polymer coatings from initial NC (a) and NC modified by a thixotropic
additive (b).

oil. The character of structure formation is changed significantly in the development of a


thixotropic structure, which is also indicated by the change of the rheological properties. It
is seen that solutions of initial NC and polyurethane oligomers represent weakly-structured
or Newton-type systems. Their modification by castor oil and weakly branched oligomers
does not change the character of the rheological curves. Formation of a thixotropic structure
is observed in a solution of NC in the presence of a highly branched oligomer. The cause
of this phenomenon was shown by the method of IRS to be related to the formation of hydrogen bonds between hydroxyl groups of NC and the modifier.
These regularities were used to produce a thixotropic structure in solutions of polymers of different chemical composition with the view to improve the properties of polymer
coatings: polyurethanes, polyester amidourethanes, chlorinated rubbers, nairites and chlorinated nairites, block copolymers (Fig. 3.2) .
Depending on the purpose of polymer coatings, the thixotropic structure can be formed
by choosing the nature of solvent; introducing a surfactant with a definite structure of mol4

1
2

log

4
3
1

0
1

log p
Figure 3.3 Dependence of viscosity on shearing stress for 10% solutions of the initial components
(a) and modified NC (b): a, for strongly (1), medium (2), weakly (3) branched oligomers and initial
NC (4); b, for NC modified by weakly (1), medium (2), strongly (3) branched oligomer and castor
oil (5).

CHAPTER 3

109

ecules, bifunctional compounds of polymers forming a network skeleton on solutions of the


base polymer, monomer or oligomer (Fig. 3.3).

3.2

Moisture-resistant packaging materials based on cellophane

3.2.1 Justification of the composition of the coating


Compositions based on modified cellulose became widespread in food industry as packaging materials. This is due to the fact that packaging of food products into polymer materials
significantly extends their shelf life, reduces losses in transportation and its costs. Besides,
most film materials are transparent, they colour well and take up ink printing, which enables
presenting a packaging in a good marketable state.
One of the most widespread film polymer materials is hydrated cellulose film, cellophane. It has such valuable properties as a high mechanical strength, gas impermeability,
grease resistance and transparency. However, it also has a number of drawbacks, which significantly restrict its applications. In an elementary link, the hydrated cellulose macromolecule has three hydroxyl groups, which is the cause of a large affinity of cellophane to water.

H
C

CH2OH

OH

OH
H

H
OH

OH

C
H

CH2OH

H
C

A film from hydrated cellulose contains up to 12% of water and about 11% of glycerol.
Its thickness is from 20 up to 50 m and its mass is 30100 g. To make cellophane hydrophobic, films are lacquered with a layer of 24 m cellulose ester or a synthetic polymer.
Swelling in water for 1 h by about 50%, cellophane loses its mechanical strength twofold. Besides, not being a thermoplast (and degrading when heated up to 170180C), cellophane is not capable of heat sealing, which makes impossible its use for vacuum
packaging. Various currently used modifications of cellophane are devoid of its major
drawbacks. Until recently, the basic coating for cellophane was nitrocellulose. However,
these coatings have a comparatively low adhesion to hydrated cellulose (especially in a humid atmosphere); low heat sealability, grease and oil resistance; become more vapour- and
moisture-permeable upon application of labels.
Lacquered cellophane used in Russia, by the company Meyer, also has nitrocellulose
as the base for the coating. Along with the general drawbacks characteristic of cellophane
with such a kind of coatings, cellophane by Meyer also has the following drawbacks. The
lacquer composition is multi-component (over 10 components), many of the components
have not been disclosed by the company and are not manufactured by Russian industries.
Domestic research yielded a moisture-resistant, heat-sealable cellophane with a coating based on domestic raw materials; optimal processes for it have been worked out.
To develop moisture-resistant heat-sealable cellophane, thermoplastic polymers with
high parameters of moisture resistance were used as modifiers: copolymers of vinylidene

110

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

chloride and vinyl chloride, epoxy oligomers with molecular masses from 600 up to 3000
and various compositions on their basis.
Tables 3.23.6 present the properties of modifying polymers.
Table 3.2 Properties of films from copolymers of vinylidene chloride with acrylonitrile at ratios
of 80:20 and 60:40.

Ratio of monomers in initial mixture


(vinylidene:acrylonitrile)
Content of nitrogen in copolymer, %
Content of acrylonitrile, wt. %
Characteristic viscosity in cyclohexanone
Gas permeability of 25-m film, ml/645 cm2 /24 h/atm
for N2
for O2
for CO2

F-218

F-220

80:20
6.1
23.1
0.95

60:40
1.2
42.4
1.87

0.084
0.710
1.770

0.422
3.420
7.910

Table 3.3 Basic properties of resin Saran F-120 (copolymer with a high content of vinylidene
chloride and low content of acrylonitrile).
Properties

Grades of different viscosity

Viscosity limits, cp
Specific weight at 25C
Refractive index at 25C
Tensile strength, MPa
Elongation, %
Moisture permeability of films, g/dm2 24 h at 37C
Permeability of toluene vapours, g/dm2 24 h

210 3 Pas

10 3 Pa h

180220
1.60
1.580
56
8
0.023
0.0403

10120
1.60
1.580
70.3
8
0.023
0.0403

Table 3.4 Properties of films from copolymers of vinyl chloride, vinylidene chloride, and from
epoxy oligomers.
Water
resistance

Oil/grease
resistance

80100

excellent

good

100150

excellent

excellent

2000

115160

excellent
excellent

excellent
unstable

Gas permeability
Heat
for O2, 10 6 g
sealability
mm/244 m2 cmN temperature,
at 21C, 0% rel.
C
humidity

Material

Water
permeability,
g mm/244 m2
cm Hg at 25C

Copolymer of
vinylidene chloride
with vinyl acetate
Copolymer of
vinylidene chloride
with vinyl chloride
Epoxy oligomers
Low-density polyethylene

0.20

0.01

0.06

111

CHAPTER 3

Table 3.5 Characteristics of copolymers.


Name of polymer

Relative humidity

Content of C, %

Copolymer of vinylidene chloride with


acrylonitrile at a ratio of 80:20 [SVN-80]
60:40 [SVN-60]
Copolymer of vinylidene chloride with
vinyl chloride at a ratio of 60:40 [SVKh-40]
Copolymer of vinyl chloride with vinyl
acetate [VKh+VA]

1.59

57.98

2.49

1.29

50.88

Table 3.6 Characteristics of epoxy oligomers.


Epoxy
grade

ED-5
ED-15
E-40

Mol. mass

Epoxy
value,
%

1620
57
1820

12

10
710
18

54

910
67
24

60
7080
150

10
6
3

30
18
9

600

E-41
E-44
E-49

900
1500
2500
3000

Viscosity*, Amount of hardener Melting Elasticity


sec
per 100 g of
temperaby the
oligomer
ture (ring
NIILK
and ball
scale**
hardener adduct
test),
No 1
C

25 by
Ubbelode
7280
8590
105

Solvents

510

ketones
ketones
toluene

150
150
540

acetates
ketones
ketones,
ethyl
cellosolve

*of a 40% solution in cellosolve, as measured by a VZ-4 viscosimeter.


**NIILK = Nauchno-Issledovatelsky Institut Lakov i Krasok = Research Institute of Lacquers and
Paints

Polyvinylidene chloride is a very strong and robust material with exceptionally good
water resistance, it has a high softening point, as well as a limited compatibility and solubility. Copolymers of vinylidene chloride with such monomers as acrylonitrile or vinyl
chloride have a slightly lower water resistance and chemical resistance than polyvinylidene
chloride; however, they possess a good solubility and compatibility. These copolymers are
applicable for production of coatings, films, sheets and plastics.
Table 3.7 presents the properties of films from copolymer SVN-80 produced by casting from solution in methyl ethyl ketone.
Table 3.7 Properties of CVN-80 films (thickness, 70 m).
Tensile strength,
MPa

Relative
elongation,
%

Vapour / moisture
permeability,
g/dm2 (48 h)

Air permeability,
cm3 cm/cm2 sec atm

20

280

0.035

0.04010 8

Swelling in water,
% (24 h)

112

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

3.2.2 Copolymer-based coatings


O
Copolymers having in their composition the polar groups Cl ; C N C
and
CH3
others were used as coatings for cellophane.
The 5% solutions of these copolymers in a mixture of acetone and cyclohexane (1:1)
were used. Lacquering was done by dipping followed by drying in the air. The material obtained was tested for vapour and moisture permeability (Table 3.8) and swelling in water
(Table 3.9).
Table 3.8 Vapour/moisture permeability of cellophane lacquered with various copolymers.
Copolymer used as a coating for
cellophane

Thickness of coating, m

Vapour

Moisture

permeability, g/dm2 (48 h)

SVN-80
SVN-60
SVKh-40
VKh+VA
Common cellophane

5
5
4.5
4.5

0.72
2.50
0.45
4.00
17

0.82
2.00
0.65
16.00
25

As it follows from Table 3.8, the greatest effect in decreasing vapour and moisture permeability of cellophane was rendered by copolymers SVN-80 and SVKh-40.
Table 3.9 Kinetics of swelling in water of cellophane lacquered by various copolymers.
Copolymer used as a
coating for cellophane
SVN-80
SVN-60
SVKh-40
VKh+VA
Common cellophane

Thickness
of coating,
m

Weight increment, %
1h

2h

3h

5h

24 h

Film
peeling
time

5
5
4.5
4.5

17.0
25.0
60.0
48.0
70.0

29.0
32.5

75.0
75.0

34.5
38.0

78.0

34.5
45.0

80.0

60.0
70.0

85.0

48 h
24 h
20 min
2h

As it follows from Table 3.9, cellophane with a lacquered coating from SVN-80 possesses a lower degree of swelling in water in 24 h. The film of this copolymer peels off cellophane in 48 h, whereas the film SVKh-40, which also provides for a sufficiently low
vapour and moisture permeability of cellophane, peels off in 20 min of swelling in water.
Figure 3.4 presents the kinetics of swelling in water of common cellophane and cellophane lacquered with copolymers SVN-80 and SVN-60. Common cellophane swells in 1
h almost to a maximum, and then in 24 h the amount of absorbed moisture increases insignificantly. In the case of coating with lacquers, the swelling in 1 h decreases by about 5
times for the coating from SVN-80 and by about 3 times for the coating from SVN-60. In
only 24 h the swelling of lacquered cellophane reaches a maximum of 6070%.
Studies have shown that lacquered coating from copolymer SVN-80 is the most expedient material to be used as a hydrophobic coating for cellophane.
Various epoxy polymers with molecular masses from 600 up to 3000 were used to obtain water-resistant coatings for cellophane. Various solutions of epoxy oligomers (10, 15

CHAPTER 3

Weight increment, %

100

113

80

2
3

60
40
20
0
2

10 12 14 16 18 20 22
Swelling time, h

Figure 3.4 Kinetics of swelling in water of common cellophane and cellophane lacquered with
SVN: 1, common; 2, SVN-60; 3, SVN-80.

and 20%) in a mixture of acetone and cyclohexane (1:1) were prepared. Cellophane was
lacquered by dipping followed by drying in the air. The hardeners used were polyethylene
polyamine, hardener No 1 (a 50% solution of hexamethylene diamine in alcohol) and adduct. The materials produced were tested for vapour and moisture permeability and swelling in water (see Table 3.10, Figs. 3.53.8).
Table 3.10 Vapour/moisture permeability of cellophane with epoxy coatings.
Epoxy grade

Molecular mass

E-40

600

E-41

900

E-44

1500

E-49

3000

Concentration
of lacquer, %

Vapour

20
15
10
20
15
10
20
15
10
20
15
10

1.60
1.73
1.80
1.59
2.00
2.50
1.82
2.22
2.70
1.50
2.10
2.70

Moisture

permeability, g/dm2 (48 h)


1.45
1.70
1.63
1.40
1.80
2.08
1.45
1.80
2.60
1.45
2.04
2.96

Cellophane with coatings from epoxy oligomers possesses a good heat sealability.
However, it appears not possible to recommend epoxy coatings for cellophane, as thicker
coatings (~10 m) are required to achieve the required hydrophobic properties, which leads
to a considerable decrease of the elasticity of material on the whole and, besides, to cracking
and pitting of the coating, both in the sites of sealing and on the surface of the material in
comparatively small storage times.

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Gas permeability, g/dm2 48 h

114

1
4

10
8
Thickness of coating, m

Moisture permeability, g/dm2

Figure 3.5 Dependence of vapour permeability of cellophane with coatings from various epoxy oligomers on the thickness of a coating.

E-49
E-40
E-41
E-44

2.5

10
7.5
Thickness of coating, m

Weight increment, %

Figure 3.6 Dependence of moisture permeability of cellophane with coatings from various epoxy
oligomers on the thickness of a coating.

E-40
E-44
E-49

40
30
20
10
0
0

10

20
15
Concentration of lacquer, %

Figure 3.7 Dependence of the swelling in water for 1 h of cellophane with various epoxy coatings
on the thickness of a coating.

CHAPTER 3

115

Swelling, %

50
40
30

E-40
E-41
E-44
E-49

20
10
1

24
Swelling time, h

Figure 3.8 Kinetics of the swelling in water of cellophane with an epoxy coating; concentration of
a lacquer, 20%.

3.2.3 Coatings based on lacquer compositions


With the aim to eliminate the drawbacks specific to copolymer coatings and those based on
epoxy polymers, works were carried out to develop and adjust lacquer compositions based
on SVN-80 and E-49 polymers imparting cellophane with the most hydrophobic properties as compared with other polymers studied.
Lacquer compositions were prepared as follows. Dry resin E-49 in the amount of 50,
30, 20, 10 and 5% of the weight of dry copolymer was added into a 3% solution of SVN-80
in a mixture of acetone and cyclohexanone (1:1). Cellophane was lacquered by dipping and
dried in the air. The coating produced had (depending on the amount of epoxy oligomer
added, see above) the following weight per 1 m2: 7.0 g, 5.0 g, 5.0 g, 5.0 g, 4.5 g.
If the specific weight of the coating is taken to be ~1 g/cm3, then the thickness of the
lacquer layer (on two sides) is equal, respectively, to 7 m, 5 m, 5 m, 5 m, 4.5 m. The
coating obtained was thin, elastic, transparent and was even along the thickness. Tables
3.11, 3.12 and Figs. 3.9, 3.10 present the data of the tests of produced material for vapour
and moisture permeability and swelling in water.
Table 3.11 Vapour and moisture permeability of cellophane lacquered with compositions from
SVN-80 and E-49.
Amount of epoxy E-49 in the
lacquer composition, %

Vapour

50
30
20
10
5

2.00
2.05
2.01
1.80
1.89

2.14
2.21
2.02
1.60
1.25

1618

2225

Nonlacquered cellophane

Moisture

Note

permeability, g/dm2 (48 h)


E-49 is introduced as a
percentage of the weight of
dry copolymer SVN-80.
Lacquer SVN-80, of 3%
concentration

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Vapour / water permeability,


g/dm2

116

4
3
2

Water permeability
Vapour permeability

10

20

30
40
50
Amount of resin E-49, %

Weight increment, %

Figure 3.9 Dependence of the vapour/moisture permeability of lacquered cellophane on the composition.

60
1

50
20

2
10

10
20
30
40
50
Content of resin E-49 in the composition, %

Figure 3.10 Change of swelling of lacquered cellophane depending on the content of resin E-49 in
the lacquer composition. 1, Swelling in 24 h; 2, swelling in 1 h.

Table 3.12 Swelling kinetics of cellophane lacquered with compositions from SVN-80 and E-49.
Amount of epoxy E-49 in the lacquer
composition, %

Weight increment, %
1h

2h

3h

5h

24 h

50

12

15

21

26

50

30

11

15

20

26

48

20

9.5

14

20

26

47

10

9.0

14

19

24

47

11

20

23

30

53

68

68

71

75

80

5
Nonlacquered cellophane

Seam strength, g/25 cm

CHAPTER 3

117

160
140
120
100
80
60
40
20
110

130

150

170

230
190
210
Temperature, C

Figure 3.11 Dependence of the seam strength of the lacquered cellophane-based composition on
temperature.

As it follows from the presented tables and figures, an optimal amount of resin E-49
in the lacquer composition, providing for the best hydrophobic properties of cellophane, is
10% of the weight of copolymer. An increase of the concentration of E-49 in the lacquer
composition leads to a deterioration of the moisture resistance of cellophane, probably, due
to a reduction of compatibility of the resin with SVN-80. A decrease of the content of E-49
down to 5% and less leads to a decrease of adhesion of the coating to cellophane (peeling
of the lacquer film on the second day, as compared with five days for compositions with
10% of E-49 and more), which, in turn, causes a deterioration of the moisture resistance of
lacquered cellophane.
Table 3.13 Dependence of the heat-seal strength of lacquered cellophane on heat sealing
temperature.
Voltage at the heat sealing
device, volts

Sealing temperature, C

Seam strength,
g/25 cm

80

130

80

160

135

180

149

85
90
95
100
110
120

170
205

131

Cellophane lacquered with a composition from SVN-80+E-49 heat seals well. An optimal heat sealing temperature is 180C (see Fig. 3.11 and Table 3.13).

118

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

3.2.4 Design of heat sealed seams


The effect of temperature on the strength of various designs of seams was studied. Two designs of heat sealed seams are known to be available: butt sealed and lap sealed (Fig. 3.12).
The former work in exfoliation; the latter, in shear.

Butt sealed

Lap sealed
Figure 3.12 Types of heat sealed seams.

Breaking strength of seam, kg/cm

Studies of the temperature dependence of the strength of heat sealed seams of these
designs showed (Fig. 3.13) the strength of seams working in shearto exceed 40130 times
the strength of seams working in exfoliation. The character of the temperature dependence
is in both cases the same: with temperature increasing the strength of the seams decreases
monotonically, which is, probably, due to the increase of the number of coating-to-base
intermolecular bonds broken per unit of time under the action of heat motion.

6
4

20

40

60

80

100 120 140


Temperature, C

Figure 3.13 Effect of temperature on the heat-seal strength of lacquered cellophane in exfoliation
(1) and in shear (2).

Seams working in shear when loaded are feasible only for longitudinal seams of most
items; butt seams work in exfoliation, thus weakening the item on the whole. It is recommended to use tucked seams (Fig. 3.14) working in shear, as they present no problems in
processing.
The diagram for the adhesion breakdown of tucked seams and a dependence of their
strength on temperature are presented in Fig. 3.15.
As it follows from Figs. 3.133.15, the breakdown character of the seams of compared
designs and the shape of the breakdown adhesiogram is absolutely the same; the absolute

CHAPTER 3

119

Initial appearance
of sealed films
Tuck
Sealing
After loading

Breaking strength of seam,


kg/cm

Figure 3.14

4
3
2
1
20

Figure 3.15

40

60

80

100 120 140


Temperature, C

Effect of temperature on the strength of tucked seams.

values of the adhesion strength of the seams are also very close.
By the performance properties and breakdown mechanism, the recommended seam
design does not practically differ from the characteristics obtained in seam shear tests.
Thus, the most rational composition from the viewpoint of heat sealability and hydrophobicity of cellophane out of copolymers with epoxy resins studied as coatings is the
lacquer composition from copolymer SVN-80 and epoxy resin E-49 in the amount of 10%
of the weight of copolymer. Cellophane with this coating was called cellophane SVN-80.
As it follows from the data of Table 3.14, the composition of copolymers SVN-80 from
various test batches is sufficiently homogeneous by its main characteristics. Thus, the ultiTable 3.14 Chlorine content and characteristic viscosity of various test batches of copolymer
SVN-80.
Batch numbers
of SVN-80

Chlorine content,
%

Characteristic
viscosity, m2/sec

Note

266/1

56.50

1.22

267/1

55.72

1.20

267/5

55.77

1.11

The characteristic viscosity of


copolymers was determined from
0.5% solutions in cyclohexane at
T = 25C

270/5

56.85

1.27

120

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Table 3.14 Chlorine content and characteristic viscosity of various test batches of copolymer
SVN-80.
Table 3.14 (continued)
Batch numbers
of SVN-80

Chlorine content,
%

Characteristic
viscosity, m2/sec

334/5

54.47

1.10

341/5

57.10

1.13

341/5

56.61

1.22

544/5

56.27

1.15

545/5

56.85

1.08

548/5

59.74

1.18

550/5

58.78

1.12

Note

mate difference in the characteristic viscosity is about 0.2, and in the content of chlorine
about 5%. For this reason, the properties of cellophane lacquered with copolymer SVN-80
in these test batches are also sufficiently homogeneous (see Table 3.15).
Table 3.15 Properties of cellophane lacquered with copolymer SVN-80 from various test batches.
SVN-80
batch nos

Vapour

Moisture

permeability, g/dm2
(48 h)

Swelling
in water,
%
(24 h)

Time to
peeling,
min

Seam
strength,
g/2.5 cm

266/1

0.16

0.17

30

50

200

267/1

0.18

0.16

35

60

200

267/5

0.11

0.13

30

50

150

270/5

0.12

0.17

30

60

150

334/5

0.10

0.10

30

60

150

341/5

0.12

0.13

35

60

200

541/5

0.17

0.19

25

50

110

544/5

0.17

0.20

35

60

100

545/5

0.18

0.20

35

60

110

548/5

0.20

0.25

35

60

120

550/5

0.14

0.17

30

60

150

Note

1. Cellophane was
lacquered with 5%
solutions of SVN-80 =
E-49 in cyclohexane
(viscosity, sec, by VZ-4
viscosimeter)
2. Tensile strength and
relative elongation of
cellophane lacquered
with SVN-80 was within
the limits of GOST (State
Standards) in all batches
studied
3. Time to peeling in
minutes was determined
by the method of GOST
7730-63

Thus, the studies conducted make it possible to conclude that the test batches of copolymer SVN-80 manufactured by the plant of the V.A. Kargin Institute of Chloroorganic
Products and Acrylates differ little from one another by their main characteristics, which
provides for the production of lacquered cellophane with sufficiently close values of the
major physicochemical and physicomechanical characteristics.

121

CHAPTER 3

3.2.5 Justification of the choice of solvent


The properties of the produced coating are known to depend largely on the quality of the
main film-forming material. However, a number of technological factors, the formulation
of the coating including, also have a significant effect on the properties of the film.
When developing the formulation of a lacquer coating, special attention should be paid
to the correct choice of the solvent for the film-forming polymer.
As it follows from the literature data, the most suitable solvents for copolymers of vinylidene chloride with acrylonitrile are ketones: methyl ethyl ketone, acetone, cyclohexanone, as well as 1,4-dioxane, dimethylformamide, mesityl oxide.
A number of solvents and solvent mixtures were tested in order to choose solvents for
the lacquer composition based on SVN-80. As expected, ketones proved to be the best; what
is more, acetones or aromatic hydrocarbons could replace 60% of ketones in the solvent
mixture. The composition would not dissolve in acetones only. The data on the choice of
solvents are given in Table 3.16.
Table 3.16 Solubility of the composition SVN-80+E-49 in various solvents (concentration was
taken in terms of three parts of SVN-80 plus 0.3 g E-49 for 100 ml solvent).
Solvents

Ratio

Solvent
boiling
temperature, C

in 1 h

in 24 h

Acetone

56

slight residue

total dissolution

Methyl ethyl ketone


Cyclohexanone
Ethyl acetate

80
156
75

total dissolution
slight residue
partial
dissolution
ditto
not dissolved
ditto

ditto
ditto
partial
dissolution
ditto
not dissolved
ditto

Butyl acetate
Ethyl cellosolve
Ethyl cellosolve

125
130140
78

Methyl ethyl ketone:


ethyl acetate

1:1

80
75

Methyl ethyl ketone:


ethyl acetate

1:4

80

Dissolution

total dissolution
almost total
dissolution

total dissolution

75
Methyl ethyl ketone:
ethyl acetate:
butyl acetate

80
75
125

incomplete dissolution, slight


residue

Methyl ethyl ketone:


ethyl acetate:
butyl acetate:
cyclohexanone
1:2:1:1

80
75
125
156

almost total
dissolution

Methyl ethyl ketone:


ethyl acetate:

80
75

1:1:3

total dissolution

total dissolution

Note

1. Dissolution
temperature,
1518C
2. Introduction
of butyl acetate
into the mixture
of solvents leads
to an opaque
coating on
cellophane

122

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Table 3.16 Solubility of the composition SVN-80+E-49 in various solvents (concentration was
taken
terms(continued)
of three parts of SVN-80 plus 0.3 g E-49 for 100 ml solvent).
Tablein3.16
Solvents

butyl acetate:
acetone

Ratio

Solvent
boiling
temperature, C

3:2:3:2

Acetone:
cyclohexanone:
butyl acetate:
toluene

Dissolution
in 1 h

Note

in 24 h

125
56
56
156
125

ditto

1:1:2:1

To find a good solvent for SVN-80, we plotted the kinetics of its swelling in vapours
of such organic solvents as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate and
some mixtures of these solvents. The data are given in Table 3.17.
Table 3.17
Solvents

Weight increment, % per hour

Acetone
Methyl ethyl ketone
Cyclohexanone
Ethyl acetate
Acetone:cyclohexanone =
1:1 (mixture No 1)

41.5
33.5
2.5
18.2
12.2

49.0
42
4.2
25.5
14.2

53.5
45.5
5.4
27
15.1

60
52.5
7.5
29
17.7

92.7 100
110
118 Swelling
86
95

98.5 temperature,
27.5
42
52
60
20C
33
33
33
33
32.2
43.2 57.0 64.0

20.5

22.9

42.7

Acetone:cyclohexanone:
15.1
butyl acetate: ethyl acetate
= 2:2:2:4 (mixture No 2)

Note

52.7

68.5

Weight increment, % per hour


Cyclohexanone

12

16

22

27

32

36

17.0

39.2

47.4

69.3

84.0

108

132

149.5

188

212

Swelling
temperature,
55C

In all solvents studied, except ethyl acetale, SVN-80 swells unrestrictedly. The extent
of its swelling in ethyl acetate vapours is 33%.
The swelling of SVN-80 in vapours of methyl ethyl ketone (without comparison with
its swelling in acetone) is characterized by the highest rate in the first 24 h.
The swelling rates of SVN-80 in vapours of all solvents studied (except ethyl acetate)
become approximately the same in 24 h (Fig. 3.16).
The SVN-80 swelling rate in acetone vapours is maximal. However, the use of acetone
as a solvent of SVN-80 is not expedient owing to its high volatility and, therefore, worse
conditions of film forming. The latter statement confirmed experimentally is consistent
with the literature data.
An increase of temperature leads to an intensification of the swelling process. Thus,

CHAPTER 3

123

130

2
110
Weight gain, %

3
90
4
5
6

70
50

30
10
8

16 24 48

56

64 72

80

88

96

Swelling time, h
Figure 3.16 Kinetics of swelling of copolymer SVN-80 in vapours of some organic solvents: 1,
cyclohexanone (T = 55C); 2, acetone; 3, methyl ethyl ketone; 4, mixture No 2; 5, mixture No 1; 6,
cyclohexanone; 7, ethyl acetate.

the swelling rate of SVN-80 in cyclohexanone at a temperature of 55C exceeds that in acetone at room temperature more than twofold.
As the result of the studies, and also because
the method of drying by infrared beams, as a more advanced method as compared
with convective drying, rules out the large duration of the drying process and the possibility
of insufficient drying of the coating
application of solvents with a high boiling temperature improves the film-forming
conditions, and the use of a mixture of solvent complicates the process at the stage of recuperation of the solvents
we believe that the use of cyclohexanone as a solvent of SVN-80 is the most expedient.
3.2.6 Wetting of hydrated cellulose film with some organic solvents and solutions of
SVN-80 on the basis of these solvents
As indicated by the results of recent studies, the value of adhesion is largely affected by the
wetting of substrate with a fluid adhesion-promoting agent. By conducting studies of the
wetting of a hydrated cellulose film with such organic solvents as cyclohexanone, acetone,
some mixtures of solvents, as well as solvents of SVN-80, we thought it possible to confirm
the choice of a solvent for SVN-80, i.e., to obtain the minimal values of the contact angle
of wetting ( ) and the time of its complete spreading (Tmax) for a good solvent for
SVN-80. The study conducted has shown that in the case of the above solvents we have an
ideal wetting of the base: is practically equal to zero, and the spreading of a drop of a
solvent is almost instantaneous. Based on these data, it was natural to assume that the affinity of the studied solvents to cellophane is almost the same, which was confirmed by the

124

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

study of the wetting of a nonpolar (paraffin) support by the same solvents. The data of the
study are summed up in Table 3.18.
Table 3.18 Contact angle of wetting of paraffin by some organic solvents.
Solvents

Acetone

Cyclohexanone

Mixture No 1

Mixture No 2

eq

37

40

43

40

As seen in the table, the values of in all four cases are rather close.
As the study of the wetting of cellophane by pure solvents gave us no possibility to
determine, which solvent is the best for SVN-80, we studied the wetting of cellophane by
solutions of SVN-80 on cyclohexanone and mixture No 1. Acetonic solutions of SVN-80
were not studied as solutions on a volatile solvent, which deteriorated film formation. The
purpose of this study also aimed at establishing the effect of the concentration of the solution on the wettability of the support. The results are presented in Tables 3.19 and 3.20 and
in Fig. 3.17.
Table 3.19 Contact angles of wetting of cellophane by solutions of SVN-80.
Contact angle of wetting, deg
T, sec

10
30
60
90
120
150
180
210
240
300
360
420
480
510

Solution of SVN-80 in cyclohexanone

Solution of SVN-80 in mixture No 1

20%

15%

10%

7.5%

5%

15%

10%

45
32
28
24
20

18

16.5
15.0

14.5

39
21
16.5
11.5
12.4
10.0
7.5

7.3

7.2

7.2

20
[75] 15
12
9
7
5

23
16
10
7
[135] 6

3.5

[15] 15
[25] 10
[35] 8.5
[40] 6.0
[50] 4.0
[60] 3.5
[90] 2.5

38
27

20

17

12

26
[25] 19
[35] 12
[45] 9
[55] 8
[110] 7

11

Table 3.20 Dependence of the contact angle of wetting and time of complete spreading on the
concentration of SVN-80 solutions.
Concentration
of solution,
%
20
15

eq, deg

Teq, min

SVN-80 in
cyclohexanone

SVN-80
in mixture 1

SVN-80 in
cyclohexanone

SVN-80
in mixture 1

15
7.5

11.0

5
4

CHAPTER 3

Table 3.20 Dependence of the contact angle of wetting and time of complete spreading on the
Table
3.20 (continued)
concentration
of SVN-80 solutions.
Concentration
of solution,
%

eq, deg
SVN-80 in
cyclohexanone

10
7.5
5

125

Teq, min

SVN-80
in mixture 1

4
3
2.5

SVN-80 in
cyclohexanone

7.0

3
2.5
1

SVN-80
in mixture 1
1

As it follows from Fig. 3.17, the rate of reaching eq is higher for the solution of
SVN-80 in mixture No 1. This is explainable by a decrease of the viscosity of the solution
at the addition of acetone to cyclohexanone. However, an increase of the rate of spreading
does not lead to an improvement of wetting. What is more, introduction of acetone worsens
the wettability of the solution. Indeed, if the value of eq in the case of the solution of
SVN-80 on cyclohexanone at a concentration of the solution of 15 and 10% is, respectively,
7.2 and 4.0, then for solutions of SVN-80 of the same concentration on a mixture of solutions, eq is 11 and 7.

Contact angle of wetting, deg

50
In cyclohexane
In mixture

40
30
20
10

10%
5%
1

10%
7.5%
3

15%
15%

5
6
Spreading time, min

Figure 3.17

This, we have shown that solutions prepared using a mixture of solvents have a worse
wettability as compared with solutions of cyclohexanone.

3.2.7 Working-out of an optimal process regime for producing cellophane SVN-80


The effect of drying time on the properties of lacquered cellophane was initially studied on
specimens obtained in the laboratory. Cellophane was lacquered by dipping*, dried in the

*3% solutions of SVN-80 and E-49 in a mixture of cyclohexanone:acetone (1:1) were used for the
coating.

126

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

air until tack-free, and then held at a temperature of 8085C for 15, 30, 45, 60 and 90 min.
It was noted that only the specimens dried for no more than 1520 min preserve their
elasticity; the others become brittle and, when allowed to swell in water, the lacquer film
in them exfoliates in several hours.
The initial variant of the pilot-plant lacquer installation for drying the coating made
use of the convective method. However, attempts to produce material with a desirable set
of properties failed: at comparatively low drying temperatures (70C) the coating peeled
off from cellophane swollen in water for 13 h; at higher drying temperatures, the coating
possessed a sufficiently good moisture resistance but was not heat sealable. Exfoliation of
the lacquer coating from cellophane swollen in water (in the case of its drying at low temperatures) can, probably, be explained by the presence of traces of solvent; the same is indicated by the opacity of lacquered cellophane in swelling. The inability of lacquered
cellophane dried at increased temperatures to be heat sealed is, probably, due to the
crosslinking of the polymer at these temperatures. At some intermediate temperatures there
is no crosslinking and no traces of solvent in the film; still, swelling in water for a short time
leads to exfoliation of the lacquer coating from cellophane.
Using the convective method, the coating is dried unevenly with respect to the thickness; the rate of diffusion of the solvent from the deep layers of the coating to the surface
layers is much smaller than the rate with which the solvent evaporates from the surface. As
the result, the surface layer dries up faster, and the solvent, which continues to diffuse to
the surface, disturbs the integrity of the coating. Micropores are produced, via which molecules of water during the swelling freely penetrate into the coating, to cellophane; its swelling exfoliation of the lacquer film occur. In the given case, these phenomena play an even
greater role owing to the fact that the solvent for the lacquer composition was a mixture of
acetone and cyclohexanone (1:1) with different boiling and evaporation temperatures.
On the other hand, the film-formation conditions are, probably, such that adhesion
forces are commensurable with internal stresses generated in the lacquer film in its formation, which can lead to rapid exfoliation of the coating in swelling.
In view of this, the convective method of drying the coating in the pilot-plant installation was replaced by a more advanced method of drying with infrared beams, which provide
for the heating of the lacquer layer along its thickness and an increased solvent diffusion
rate from the depth of the coating to the surface. Besides, IR drying removes the necessity
of using mixtures of solvents with different boiling temperatures. The high drying rates
in this method enable using cyclohexanone to produce a lacquer composition; cyclohexanone provides for good film-forming conditions and end material with an optimal set
of properties.
Preliminary works on IR drying of lacquered cellophane showed the appropriateness
of using this method of drying. Lacquered cellophane dried for 23 min by plate-type IR
radiators at an optimal distance of 5 cm between the film and the plates, at a supplied voltage
of 100 V (approximately, a temperature of 10120C corresponds to this voltage) swells
in water in 24 h up to 2023% as compared with 3540% for lacquered cellophane dried
by the convective method. The lacquered film does not peel off from cellophane swollen in
water for 5 days; the lacquered cellophane is heat sealable.
A technological scheme for producing lacquered cellophane was developed.
Cellophane from the unreeling device via the guiding rolls is fed to the lacquer bath,
where it is covered with lacquer on one or both sides as required, is then supplied to the
drying section, and after drying of the end material is supplied by a special tensioning
device to the reeling roll.

CHAPTER 3

3.3

127

Modification of cellulose diacetate for packaging materials

Films and consumer containers based on cellulose diacetate (CDA) are promising ecologically safe materials intended for contact with high fat-content spreads, confections and infants food products. Great importance of these materials for food industry and the diversity
of requirements imposed on them makes it necessary to develop new formulations of ethrols
with specific balanced sets of properties.
The possibility of targeted regulation of the properties of cellulose acetate compositions was studied. The aim of the studies was to obtain food-grade ethrols with a wide range
of plasticity properties, MFI (melt fluidity index), a wide interval between the yield temperature and breakdown temperature, a high tensile yield strength, a certain set of performance characteristics. Therefore, it was necessary to develop ethrol whose process
characteristics would enable its reprocessing into consumer containers by injection molding, by methods of blow molding and pressure forming.
We studied triacetine (TA)-placticized CDA with the content of combined acetic acid
of 55.8% and molecular mass of 45,000 (as determined from the viscosity of solutions in
acetone). Dibutyl esters of the general formula
C4H9

ROC (

CH2

)n C

where R =

CH2CH2

CH2CH2

]m

OC4H9,

or

CH2

CH
CH3

served as modifiers of the plasticizing system. Namely, they are dibutyl esters of polydiethylene glycol adipinate (PDEA), of polyethylene glycol cebacinate (PAC-22) and of
polypropylene glycol adipinate (PPA-4). The amount of modifier in the plasticizing system
of TA + oligoester was varied from 0.1 up to 10%; the amount of mixed plasticizer was
constant and equaled to 35% per 100% CDA. The ingredients were mixed in a high-speed
turbomixer at a temperature of 343 K; the mixing time of dry components was 8 min; of
dry components with liquids, 12 min. The mixture obtained was homogenized in an extruding-and-kneading machine at a melt temperature of 453 K at the outlet from the head of the
extruding machine. The straps obtained were cooled, cut into granules and used to form a
band 3540 m thick on an extruder with the orifice slit, at a temperature for the cylinder
zones of 438451468 K, orifice temperature of 468 K, temperature at the output 453 K.
Test specimens of corresponding sizes were cut from the band in longitudinal and transverse directions. Model thin films (20 m thick) from the CDA + TA + oligoester system
were prepared by hot pressing at 423 K and pressure of 12 MPa.
The phase transitions in plasticized compositions were determined by the refractometric method by finding the temperature dependence of the refractive index for thin (20 m)
films in an URL-1 refractometer at a continuous change of temperature at a rate of 1 K/min.
The glass transition temperature was determined by the thermomechanical method at a constant strain on a specimen (1.410 2 Pa) and a rate of 1 K/min and also refractometrically.
Preliminarily, the data obtained by both methods were shown to correspond one to the other.
The thermomechanical characteristics of the compositions were determined using a tensile
creep-measuring instrument according to State Standard GOST 18197-72 at a constant
strain (110 Pa) and heating rate of 5 K/min on specimens of 1.82.00.3)10 4 m.

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

The mechanical properties of model thin films were assessed on an N-2001 R-0.5 tensile tester at a strain rate of 0.3210 3 m/h with the automatic recording of the strain curve.
The mechanical indices of the extrusion films were determined at temperatures of 293 and
393 K on an Instron tensile tester according to GOST 14236-81 at a strain rate of 10 2 m/h
on specimens with the working area parameters of (5100.4)10 3 m.
The melt fluidity index MFI was determined by GOST 11645-73 on an IIRT instrument at a temperature of 463 K, load of 100 N, standard capillary of 0.948 mm in diameter
and 8 mm in length. The rheological properties of the material were studied on a capillary
constant-pressure viscosimeter at temperatures of 453, 463, 473 K and the rate of shear from
10 3 up to 10 4 s 1.
Due to the great importance of the performance stability at given temperatures in contact with biochemically active media during the development of plasticized compositions,
one should account for their thermodynamic stability. It provides for a long-time invariability of the properties not only in reprocessing, but also in long-term storage. In this connection, phase diagrams were obtained for triple CDA+TA+oligoester system of different
molecular nature (PDEA, PAC-22, PDEC, PPA-4), which made it possible to single out regions of homogeneity at various temperatures. Studies of the isothermal cross sections of
phase-equilibrium bulk diagrams have established that the homogeneity region for all systems studied expands with temperature increasing. Comparison of the phase diagrams of
the systems containing various-structure oligomers shows that an increase of the length of
aliphatic segments between ester groupings, which provide for the interaction with polar
groups of the polymer, leads to the deterioration of compatibility. Compatibility of the components of the CDA+TA+oligoester triple systems decreases in the sequence PPA-4 >
PAC-22 > PDEA. Analysis of the phase diagrams shows that at room temperature the systems comprising >57% of oligoester in the mixture are microheterogeneous.
By the example of the CDA+TA+oligoester systems, we considered the effect of oligoester on the efficiency of the plasticizing action of the TA+oligoester mixture with respect to CDA. For this purpose, we studied the concentration dependence of Tg and the
mechanical properties of the films. As the content of oligoester in the plasticizing system
increases, its plasticizing action rises. Herewith, addition of oligoester, which contains residues of molecules of sebacinic acid (up to 50% PAC-22), decreases Tg of the polymer to
a greater extent. Comparison of the phase diagrams and of the dependence Tg = f(Cm) shows
that interstructural plastification in the microheterogeneous system begins at the introduction of oligoesters. Therefore, a decrease of the extent of polarity of the components as the
result of the increase of the length of aliphatic fragments or a change of their branching in
the oligoester enhances the action of the second plasticizer, which plays the role of an interstructural lubricant leading to a large decrease of Tg.
When analysizing the data for the mechanical properties of model films from
three-component systems (Table 3.21), it is seen that the systems containing PDEA and
PPA-4 have the greatest breaking strength p; while the systems with PAC-22 are more
elastic (have a greater relative breaking elongation ). The studies conducted enabled singling out homogeneity regions for all systems studied. The regularities obtained were used
in developing food grades of ethrol with given rheological, strain-resistant and sanitary-chemical properties. Modified ethrols were fabricated by the traditional process.
The set of technological and performance properties of films fabricated from ethrol
compositions of various formulations (Table 3.22) was studied. In the general case, introduction of oligoester to an ethrol composition at the stage of its preparation significantly
(by an order of magnitude) decreases the effective viscosity of the melt, shifts Tg and Tm to

129

CHAPTER 3

the region of higher temperatures practically without changing the plasticity interval. As the
result of the decreased strength of the intermolecular bonds the deformability of the material
at increased temperatures increases. The obtained regularities were used when choosing the
optimal content of modifier in the plasticizing system to provide for a balanced set of technological and operational properties of ethrols of various purposes.
Table 3.21 Strength properties of CDA films plasticized by TA in a mixture with oligoesters
(15%).
Oligoester

TA:oligoester mass ratio

p, MPa

, %

3:1
1:1
1:3
3:1
3:1

5.6
4.2
8.7
7.1
4.1

4.5
13.0
6.0
4.5
12.0

PDEA
PDEA
PDEA
PPA-4
PAC-22

Comparative analysis of the rheological properties of base ethrol and ethrol modified
by PPA-4 showed that the optimal temperature of plasticizing material in an extruder was
438 K for the extrusion grade and 463 K for the blow-molding grade. These temperatures
provide for an intensive agitation of the melt at lower loads. It should be noted that MFI for
all modified compositions is much higher than the rated values. Such compositions can be
reprocessed at lower temperatures and smaller shear loads, which is confirmed by the data
obtained in reprocessing of modified compositions on industrial equipment.
Table 3.22 Process characteristics of modified ethrols.

p, MPa

Plasticizer and Melt viscosity,


its content, %
102, Pa s
TA (35)
TA(25)
PPA-4 (10)
TA (25)
PAC (25)
TA (25)
PDEA (10)

, %

at 293 K

at 393 K

at 293 K

at 393 K

24.0
3.5

60
40

2
4

48
42

100
140

5.2

45

20

140

5.8

45

30

130

Note: Polymer, CDA; plasticity range (Tpl Tg), 315 K.

The established anomalous dependence of the rheological, physicomechanical and


strain characteristics of modified ethrols suggests that the effect of strengthening of plasticized CDA at the introduction of small additions of oligoester is determined by structural
changes at the supramolecular level. An increase of the mobility of the structural elements
and the acceleration of relaxation processes in modified material provides for the formation
of a more homogeneous structure, which is confirmed by the data of electron-microscopy
analysis.
To determine the rational applications of packaging/container materials and consumer
containers on their basis, we determined the endurance and service time of articles in

130

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

contact with a product or a medium modelling this product (Table 3.23).


Table 3.23

Long-term strength of CDA-based specimens.

Temperature, K

293
323

Time to rupture, min


in air

in distilled water

in sunflower oil

in 3% solution of
lactic acid

6070
30

40
25

1200
1200

50
20

Note: Testing stress, 3.0 MPa.

Estimation of sanitary-chemical properties of test batches of materials and articles


from them, obtained by vacuforming and deep drawing, showed that more than 92% of the
specimens had satisfactory organoleptic parameters: a small (0.5 mg/l) dry residue, a small
amount of brominated compounds (1.55.6 mg Br/l). The amount of TA migrating to water
from ethrol-based material is 0.05 g/l; that of acetic acid, 5 mg/l; which do not exceed the
maximum permissible levels of migration.
Thus, consumer containers based on ethrol should be recommended for prepackaging
of spreads with an increased content of fat; lactic-acid products, as well as hot beverages at
their short-time effect.
3.4

Interaction of cellulose with water

Chemically, cellulose is a polymer whose elementary link is anhydro-D-glucose. The structure of the cellulose macromolecule can be represented by the following formula:
CH2OH
CH

CH2OH
O

HOHC

CH
CH

HC

OH

OH

CH2OH
O

OHC

CH
CH

CH
OH

OHC

HC
OH

O
CHOH

CH
n

OH

HC
OH

Each elementary link contains three hydroxyl groups. Two of them are secondary; one
is primary. This explains the different reactivities of the hydroxyl groups. The interaction
energies of these groups with water molecules are different, too, which would be discussed
in detail in Chapters 2 and 3. Here, we would like to note that the high hydrophilicity cellulose is due namely to the presence of three hydroxyl groups in the elementary link; these
groups interact with water molecules by forming strong hydrogen bonds.
Sorption of water by cellulose can be radically changed only by substitution of the hydroxyl groups. Indeed, a gradual substitution of the hydroxyl groups for other groups of atoms changes the sorption properties of cellulose. Thus, unetherified cellulose at 65%
relative humidity absorbs 1112% of water; cellulose diacetate, 6.5%; and triacetate, 3.2%.
Cellulose esters with a longer aliphatic residue absorb only fractions of a percent of water.

CHAPTER 3

131

The effect of the end groups of cellulose macromolecules of the sorption of water is
small, as the (number-average) extent of polymerization for common specimens of cellulose is comparatively large (greater than 200300).
Cellulose materials used in practice have natural contaminants of other polysaccharides and lignin (the satellite of cellulose in wood), which have some influence on the sorption of cellulose water; besides, there are disturbances in the chemical composition of
macromolecules of cellulose proper. These disturbances mainly consist of a partial oxidation of the hydroxyl groups in the links of chains up to carboxyl groups (without or with the
rupture of the anhydro-D-glucose ring). These partial disturbances have a small influence
on the sorption of water, but the sorption of cations from the aqueous solutions of metal
salts, e.g., the sorption of iron ions, may increase substantially.
Partial destruction of cellulose in its purification leads to a decrease of the extent of
polymerization and to the emergence of low-molecular-mass products, which can be partially soluble in water, especially at increased temperatures. Without having a noticeable
direct effect on the equilibrium values of water sorption by cellulose materials, under certain conditions this can affect the water sorption kinetics. One of the hypotheses explaining
the differences in the reactivity (kinetics of the process) during the etherification of various-origin cellulose materials is related to the account for the physical transformations of
low-molecular-mass admixtures during the drying of cellulose at high temperatures.
Though the presence of the hydroxyl groups in cellulose is a factor, which mainly determines its sorptivity with respect to water, a significant role is also played by the physical
structure of cellulose material, which has an effect on both the equilibrium values of water
absorption and on the kinetics of the sorptiondesorption processes.
First of all, it should be noted that cellulose is a crystallizable polymer. The energy of
hydrogen bonds emerging between water molecules and hydroxyl groups of cellulose
proves to be insufficient to break the crystalline lattice. Therefore, the sorption of water occurs only in amorphous regions and does not affect the crystalline regions (except the hydroxyl groups, which are on the surface and in the defect regions of the crystallites). The
extent of crystallinity of cellulose depends on the origin (prehistory) of the specimen. Natural cellulose (cotton, ramie) has the greatest degree of crystallinity. Cellulose regenerated
from solutions of cellulose and its ethers (following the saponification of the latter) has a
much lower crystallinity. Usually, the extent of crystallinity estimated from X-ray diffraction measurements is 6070% for natural cellulose and about 2540% for regenerated cellulose.
The values of water sorption differ accordingly. As a rule, the sorption of water by regenerated cellulose (viscose fibres) is approximately two times as high as that of natural
cellulose (e.g., cotton or ramie).
Alkaline and temperature treatments of cellulose can cause transitions between particular types of crystal lattices. Thus, a cellulose modification I, which occurs in natural specimens, during the transfer of cellulose into the solution followed by regeneration from
solution or during the treatment in moderate-concentration alkali and then the washout of
alkali passes into a crystalline modification of cellulose II, which differs from cellulose I
by interplane distances and angular ratios in the lattice. At increased temperatures, cellulose
II passes to a modification of cellulose IV. All these transformations, apparently, would not
have a strong effect on the sorption of water by cellulose, if they would not have been accompanied by the simultaneous changes in crystallinity. During the mercerization (alkaline
treatment) and at the regeneration of cellulose from solutions the extent of crystallinity decreases significantly, as we mentioned above. Some increase of the extent of crystallinity

132

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

occurs during the temperature treatments of regenerated cellulose in moist state, which is
accompanied by a partial transition of cellulose II to cellulose IV. This treatment leads to a
cellulose sorptivity decrease with respect to water, though the isomorphic conversion
proves to be not the determining event but a process occurring in parallel.
Cellulose can be totally amorphized by dry mechanical grinding. This can be seen from
the results of the X-ray diffraction study and from the fact that the heat of the interaction of
this cellulose with water is three to four times as high as the heat of wetting the nonground
cellulose. But the interaction with water is followed by the crystallization process, and cellulose again becomes insoluble. Incidentally, during the formation of viscose fibres in the
initial stage after the saponification of cellulose xanthogenate these fibres very strongly
swell in water (after the washout of precipitation-bath salts), but after some time the swelling strongly decreases as the result of the completion of the crystallization processes.
Besides the important role of the phase state in determining the sorption properties of
cellulose, we should also note the effect of such a factor as the physical structure of cellulose
material. The matter is that besides the true sorption of water (absorption) determined by
the amount of the amorphous component of polymer, there occurs a capillary uptake of water by cellulose materials due to porosity, which can be obvious (capillaries in natural fibres,
interfibrillar spaces in wood, pores in cells of plant cellulose and in artificial cellulose fibres, capillaries and pores in paper and textile materials) and hidden, revealed during the
wetting in water and representing the pores and capillaries, which are collapsed in the drying of moist cellulose materials and are capable of being restored due to the relaxation of
internal stresses remaining in the dry specimen.
Experiments confirming the thermodynamic nonequilibrium of real cellulose materials, which determines the dependence of the sorption properties on their prehistory, were
described.
It should be noted that this nonequilibrium renders an especially serious effect on the
kinetics of absorption processes.

4
4.1

Compositions for Decorative


Finish and Protection of
Packaging Products

Bases of the formation of protective and decorative finish coatings

Aqueous dispersions of polymers are the most promising class of film formers in paper and
printing industries, applicable for fabrication of protective and decorative coatings on packaging products.
The use of polymers aqueous dispersions has a number of advantages as compared
with solutions of polymers in organic solvents, making it possible:
to eliminate the danger of fire and to decrease occupational hazards of work
to decrease considerably the power intensity of production and to eliminate the use
of heavy equipment
in a number of cases to achieve a higher quality of articles produced.
Fabrication of polymer coatings for packaging products with a required set of properties is the final aim of using latexes or aqueous dispersions of polymers for finishing printing products. In this connection, of great importance is the quality of polymer coatings and
the mechanism of their formation.
Formation of films from polymer solutions has been studied by many researchers,
primarily by Russian scientists V.A. Kargin, P.V. Kozlov, A.Ya. Drinberg, P.I. Zubov,
S.S. Voyutsky and others.
In contrast, the formation mechanism and structure of films from polymer dispersions
have been studied insufficiently. The effect of the chemical composition, structure of latex
particles and coatings on the decorative and protective properties has not been studied; the
impact of the nature of the support, especially of fibrous materials, on the formation and
properties of latex coatings has not been studied sufficiently enough.
In works of the recent years the physicomechanical properties of the coatings have
been shown to depend not only on the chemical structure of the film former, but also on the
colloidalchemical nature of latex, size and structure of latex particles, nature and concentration of polar groups.
It follows from these data that the complex structure of latex particles, which are supramolecular formations consisting of simpler structural elements, determines the incompleteness of the relaxation processes and has an effect on the values of internal stresses, the
kinetics of their buildup and relaxation.
The specific features of polymer coatings used for finishing printing products are that,

134

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

along with good physicomechanical properties, they should have a high light resistance,
gloss and have no tackiness.
The dependence of these parameters on the structure and chemical composition of a
polymer has not been studied sufficiently. This impedes the correct scientifically grounded
choice of film formers for finishing the printing products and does not make it possible to
formulate the requirements for finishing compositions.
The effect of the chemical composition of polymer, the structure of latex particles, the
nature and concentration of polar groups, the colloidalchemical nature of latex on the formation of the coatings, decorative and physicomechanical properties (strength, adhesion,
relative strain, internal stresses) was studied. This was done by comparing the kinetics of
forming the structure and properties of the coatings on a model non-porous glass support
with the mechanisms of forming the coatings on fibrous bases of the type of offset paper
and offprints.
One of the ways to increase the quality of printed matter is application of transparent
polymer coatings on printed material, which improves its decorative appearance and increases mechanical strength.
The following requirements are imposed on polymer films on printed matter (offprints): high gloss, elasticity, transparency, absence of tack, water resistance, light permanence, stability and mechanical strength.
Application of protective and decorative coatings to the surface of printed matter is
done in two different techniques: lamination of the end polymer film to offprints and direct
application of a film former to offprints.
In application of coatings to printed matter by the latter technique, film formers of
three different types can be used, which differ significantly by their film-formation mechanism:
solutions of polymers
compositions of oligomers
dispersions of polymers.
The method of producing coatings from polymer solutions is used the most for finishing printed matter in Russia and abroad. This is due to the simplicity of producing coatings
and the absence of additional components in their composition (emulsifiers, hardeners,
etc.), which in some cases worsen the properties of the coatings.
The chemical composition of these lacquers is approximately as follows (in %):
Polymer
Plasticizer
Solvent

4050
25
5845

Amorphous polymers of the type of polyvinyl acetate, polyvinyl butyral, polyvinyl alcohol, cellulose esters etc. are mainly used as film formers.
Coatings from polymers with a large extent of crystallinity are distinguished by a high
strength, but they have not found use in finishing printed matter due to poor adhesion to the
coated surface.
The decorative and protective properties of the coatings are affected by the nature of
solvents used. The most widespread classes of solvents are alcohols, ethers and esters,
hydrocarbons, etc.

CHAPTER 4

135

The hydroxyl group confers a greater polarity and strong hydrophilicity to alcohols.
Methyl, ethyl and propyl alcohols are totally mixed with water. A decrease of hydrophilicity
with the molecular mass increasing affects the dissolving capacity. The higher members of
the homologous series, e.g., butyl alcohol, improve the flow behaviour and prevent the
blooming of films produced by application of nitrocellulose lacquers. Alcohols are rather
stable compounds and find application for many types of lacquer-and-paint materials.
Ethers, such as ethyl ether and propyl ether, in a mixture with other solvents, for instance, dissolve cellulose. These ethers are too volatile, readily form peroxides, and are used
in compositions of lacquer-and-paint materials on a limited scale.
Esters are similar to ketones by polarity, but are less hydrophilic. Formates, which are
esters of lower molecular masses than acetates, are unsuitable due to their instability, are
easily hydrolyzed by water and are too volatile. Acetates (ethyl acetate, butyl acetate, isopropyl acetate) are very widely used, especially in nitrocellulose materials.
To impart elasticity to the film, plasticizers are introduced into the solution of a film
former. Fluids with a relatively small molecular mass are usually used as plasticizers.
Earlier printed-matter finishes made use of lacquers based on natural resins of the type
of copal, wood rosin and sandarac in ethyl alcohol.
Copal is a hard resin of plant origin, of transparent yellow or reddish colour. The heat
treatment of copal at 280320C improves its solubility in ethyl alcohol as the result of
stripping volatile substances. Manila copal, completely dissolvable in ethyl alcohol, is used
for fabrication of lacquers.
Wood rosin is conifer resin; it can be of two types depending on the method of production: gum rosin and wet-process rosin. Gum rosin is produced from raw gum of conifers,
wet-process rosin is extracted from resinous wood with alkali. Wood rosin is a mixture of
isomeric monobasic rosin acids of the general formula C20H30O2. Rosin acids present in
wood rosin are a mixture of dextropimaric acid with conversion products of levopimaric
and -sapinic acids, the major of which is abietinic acid. The structure of abietinic acid is
expressed by the formula:
H3C

COOH

CH3

CH3
CH
CH3

Sandarac is an thick aromatic resin of the North-African Sandarac tree.


The approximate composition of these lacquers, in %:
Copal
Wood rosin
Sandarac
Ethyl alcohol

25.525.0
17.510.0
5.0
5760.0

Lacquers were also used for lacquering dust wrappers and other kinds of printed matter. Lacquers from imported natural resins are expensive, are produced in minor amounts
and have not found wide use in printed-matter finishing.
Finishing of printed matter in the West is done using nitrocellulose lacquers. Their formulation includes nitrocellulose, a plasticizer and organic solvents methyl alcohol,

136

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

methyl acetate, ethyl acetate, butyl alcohol, toluene, xylene.


These lacquers give high-quality coatings on chalk-coated paper. Nitrocellulose lacquers are toxic and explosive. In spite of this, they are manufactured as modified compositions on a large scale by a number of companies: Grafisk Farg (Sweden), Sadolin (Finland),
lacquer L-186; Sicpa (Switzerland), rapid-setting lacquer intended for application to offprints printed on chalk-coated paper; Herbol (Germany), gloss lacquer with high gloss of
the coating; Herberts (Germany), brilliant lacquer GL; Lorilleux-Lefrans (France), delta
lacquer and lacquer for finishing offprints printed by high-print and offset methods.
Iditol lacquer is an ethyl-alcohol solution of the product of polycondensation of phenol
with formaldehyde in the presence of a catalyst (oxalic or hydrochloric acids).
OH

OH
O

+ n HC
O

OH
CH2

OH
CH2

CH2 ...

n H2O

Coatings based on this resin are light non-permanent.


Carbinol lacquer is a solution of MBK-10 resin in ethyl alcohol. Products of polymerization and copolymerization of vinyl ethyl carbinol are called carbinol resins. Resin
MBK-10 is produced by copolymerization of dimethyl vinyl ethynyl carbinol containing
no inhibitor, with technical-grade methyl methacrylate and butyl methacrylate in the presence of benzoyl in ethyl cellosolve. Carbinol lacquer forms a glossy film with a yellowish
tint on the offprint. The lacquer has a sharp unpleasant smell, preserved in the coating even
after a prolonged drying at 80C.
Lacquer KS-235 is a solution of low-molecular-mass carbinol resin and cyclohexanone-formaldehyde resin in hydrazite. The film of this lacquer is light-permanent, elastic, but has an increased tackiness, which leads to the agglutination of offprints in a paper
sheet stack.
For finishing printed materials, home industries manufacture polyvinyl acetate
lacquer, which is a 40% solution of polyvinyl acetate in ethyl alcohol. Polyvinyl acetate is
a thermoplastic colourless transparent solid product obtained by polymerization of vinyl
acetate.
n CH2

CH
O

CH2
CO

CH3

CH
O

CO

CH3

To impart polyvinyl acetate with rubberlike properties, it is plasticized with dibutyl


phthalate. The alcoholic solution of polyvinyl acetate is used as a lacquer for lacquering offprints; it forms a light-permanent, transparent, elastic, colourless film without smell but
with a low gloss, even on chalk-coated paper.
Formation of the film from polymer solutions on the surface of printed matter is accompanied by the emergence of local physical links between the most active groups of
structural elements as the result of the evaporation of the solvent and the slowdown of the
relaxation processes.
It has been shown that the incompleteness of the relaxation processes during the formation of coatings from polymer solutions (polyvinyl alcohol and its derivatives, nitrocellulose and others) leads to the emergence of significant internal stresses reducing the service
life of the coatings.

CHAPTER 4

137

Coatings from lacquers based on polymer solutions, along with good decorative and
high physicomechanical properties, have a number of drawbacks. They contain toxic and
fire-hazardous solvents, are distinguished by the low content of dry matter at a working viscosity, poor light permanence; evoke the dissolution of alcohol-nonresistant pigments.
Organic solvents in lacquers are, as a rule, lost irreversibly, they pollute the air in production facilities and necessitate special measures to be taken on safety regulations and occupational sanitation (among solvents, aromatic hydrocarbons are poisonous).
According to the data of Western statistics, the level of occupational diseases in workers of paint shops and bays is five times and more higher than the average level in industries.
In this country, where human health is given great attention, abandonment of organic
solvents in protective coatings technology is not only a technical but also a social problem.
The use of organic solvents is a critical drawback of lacquer-and-paint materials also
because it creates problems of technological character lacquers should be diluted with organic solvents before application; this makes their compositions, dissolving capability, volatility, viscosity etc. variable.
One of the directions in solving the problem of excluding organic solvents from the
formulations of lacquer-and-paint materials is to develop aqueous lacquer-and-paint compositions, i.e., such systems, where the role of a medium determining the required conditions of applying and forming a coating is played by water.
When using aqueous lacquer-and-paint systems, it becomes possible not only to save
on the cost of irrevocably lost organic solvents, on ventilation and safety measures, to make
the painting process safe and flame-proof, but also to receive a number of technical advantages:
possibility of applying the coating at increased humidity
use of electrophoretic sedimentation, a method special for aqueous systems; in the
West, this method found use in paper-making plants in fabrication of high-gloss paper rolls
harmlessness and smaller labour intensity of cleaning the equipment
water as a solvent or dispersant is extremely convenient.
In this country, some printing plants attempted to use alcoholwater solutions of polymers, whose composition is approximately as follows (in %):
Polymer (alcohol/water-soluble)
Additives
Solvent (a mixture of water and alcohol, 1:2)

1015
510
8575

Special additives are meant to be materials, which are introduced into the composition
for hardening, crosslinking of the polymer (e.g., boric acid for polyvinyl alcohol, etc.). They
form films of high strength and good decorative properties, but the use of these polymer
solutions for finishing printed matter is made difficult due to the sharply increased viscosity
of film formers at a comparatively low percentage of polymer in the lacquer. In some cases,
this considerably affects the gloss of the film. Special additives should be introduced into
the lacquer immediately before its application to offprints, as the life time of such a lacquer
is several hours. A large amount of water in the formulation leads to the notwettability of
the most ink-saturated regions of the offprint, to a decreased adhesion to the substrate and
to a deformation of the products as the result of strong wetting. A considerable energy is
required to remove such a large amount of water, and the rate of the drying process of lacquered offprints does not correspond to the general rate of the lacquering process.

138

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

For instance, a nonexplosive and nontoxic lacquer PVSK based on polyvinyl alcohol
...

CH2

CH

CH2

CH

...

OH

OH

has been developed, with an addition of boric acid and emulsifier OP-7. The lacquer is not
in use due to the duration of drying of lacquered offprints at high temperature and their curling, although it has good decorative and physicomechanical properties (high gloss, resistance to abrasion, transparency, light permanence of the film).
Lacquers based on vinyl resins have been developed for lacquering specific kinds of
production labels and others. The lacquer PVM-1 is a solution of polyvinyl butyral with
an addition of water-soluble phenol formaldehyde film VMCh-4, whose formula is as follows:
HOH2C N CH2 N CH2 N H

HOH2C

HN

O
CH2O(CH)2OC2H5

This resin is added as a crosslinking agent to increase the water resistance of the film.
A special class of compounds for production of coatings are oligomers. Their specific
features are that the monomer present in them performs the role of a polymerizing solvent.
In film formation, it is involved in the polymerization proceeding on the support and leading
to the formation of a three-dimensional network structure. This provides for the production
of materials with a low initial viscosity at an increased concentration of the film former.
The use of oligomer systems enables a sharp decrease of the content of volatile solvents and
yields coatings with high mechanical and adhesion properties.
Oligomer compositions include oligomers and polymerizing solvents and, in some
cases, evaporating solvents. Synthetic resins (condensation polymers alkides, phenol
formaldehyde polyesters, amino formaldehyde esters, and others) are used as oligomers.
Oligomer systems are not used in pure form in printing industry for finishing printed
matter. They are used in a mixture with natural resins of the type of wood rosin, copal, sandarac and vegetable oils. Hard resins, used since long time ago in production of oil lacquers,
interact with oils by way of reetherification to form products similar to alkyds in their structure.
Thus, for instance, the lacquer for overprinting is a solution of hard resin in a mixture
with vegetable and mineral oils. Fixation of the lacquer on offprints occurs due to a partial
soaking-in of oils followed by the formation of a strong film as the result of oxidative polymerization. In spite of a number of advantages such lacquers present (lacquering can be
done typographically and by the offset method, sometimes selectively from the printed elements of the mold), they do not make it possible to produce films with high mechanical
and decorative properties in one run on papers with high absorptivity and low smoothness.
Formation of the film under normal conditions of drying is very slow, so anti-setoff preparations have to be used, offprints have to be kept in stacks not higher than 3040 cm and
shook every hour to avoid tackiness. To produce a continuous film, high drying temperature
and long drying time are required, as the mechanism of coating formation from these compositions is complex and is accompanied by the removal of solvent, by the oxidation and
polymerization processes to form the three-dimensional network. It is reported that electromagnetic waves of a frequency fro 0.3 up to 3000 Hz are used to accelerate stacking of printed materials with the aim to rapidly obtain a dry protective lacquer film on offprints.

CHAPTER 4

139

The most widespread in home industry is a lacquer (CF-1) based on an oligomer film
former the cyclohexanoneformaldehyde resin. The CF-1 lacquer is a solution of the following composition (in %):
Cyclohexanoneformaldehyde resin
Plasticizer
Colophony (pine wood rosin)
Ethyl alcohol

52
2
5
41

When used to lacquer papers with high absorptivity (e.g., offset papers), this lacquer
does not form a film with good physicomechanical and decorative properties. To impart the
coating with gloss and to increase the abrasion resistance of the offprint, two layers of lacquer should be applied, which is extremely unproductive and uneconomical.

4.2

Application of aqueous dispersions of polymers for finishing products

Aqueous dispersions of polymers have advantages in comparison with aqueous solutions


of polymers, as they enable production of film formers with a greater concentration of polymer (4050%) at a comparatively low viscosity and rapidly dry to form the film. The viscosity of dispersions does not depend on the extent of polymerization of resins.
Film formers for finishing packaging materials were chosen in two directions:
first, Russian-make aqueous dispersions of polymers were used for finishing; the decorative properties of coatings on their basis were studied
based on the analysis and studies of Western patents and literature, the most promising aqueous dispersions of polymers were chosen and recommended to Russian chemical
enterprises for the development of special compositions of latexes with account for the requirements of the qualitative finishing of printed materials and for availability of Russian
raw materials for production of latexes.
Aqueous dispersions consists of an aqueous dispersion medium and polymer dispersed
in it. Polymer dispersions used for coatings on paper are obtained predominantly in the reaction yielding high-molecular-mass substances in an aqueous medium in the process of
emulsion polymerization: in the presence of an emulsifier and an initiator.
Dispersions used the most for application of surface coatings to paper are vinyl acetate
dispersions, copolymers of this type, as well as acrylate dispersions. The company Hoechst
(Germany) manufactures an aqueous dispersion of polyvinyl acetate under the name of
Movilit for fabricating decorative coatings on paper.
Many researchers deal with synthesizing novel compositions of aqueous dispersions.
Western patents recommend an aqueous dispersion containing a linear polymer and the ammonium salt of the copolymer of diisobutylene with maleic acid monoamide. The quality
of this coating is good: butadienepolystyrene copolymers and polyacrylates can be used
for coatings on paper; DuPont (USA) manufactures a dispersion of blended polymers of
polyvinyl acetate and polyethylene under the trademarks of Elvax 150 and Elvax 250,
which form a glossy coating on printed material.
Methods of producing aqueous dispersions of polymers are different. Bayer et al. propose the following method: vinyl esters (e.g., vinyl acetate, vinyl propionate) as well as
mixtures with other polymerizing esters (e.g., esters of acrylic, maleic and fumaric acids)

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

are polymerized in a neutral or weakly acidic medium in the presence of water-soluble activators and protective colloids.
A method for producing polyvinyl acetate dispersions stable at low temperatures was
developed. The release of an aqueous dispersion of a copolymer of vinyl acetate with other
monomers under the trademark of Wallpol 9120 is reported; the formulation is used for lacquer coatings. This dispersion is produced using esters of unsaturated (maleic, fumaric) acids and acrylic-acid esters as a copolymerization monomer.
Films of polymer aqueous dispersions on paper, as well as lacquer films for finishing
printed materials, should possess certain properties: gloss, elasticity, transparency, water
resistance, light permanence, mechanical strength, stability and low-temperature resistance.
Low-viscous dispersions forming thin films (1015 m) on paper can be used for coating printed and packaging materials. The gloss of films of vinyl-polymer and polyvinyl acetate dispersions depends on the size of their particles. Coarse dispersions with particle size
of 0.52.0 m form mat coatings. Fine dispersions with particle size of 0.050.2 m form
glossy elastic coatings. Films of polymer coatings on paper are transparent.
Water resistance of polymer coatings is of great significance. Water-resistant coatings
can be produced using polymers obtained by polymerization of vinyl acetate with additions
of acrylic- or nitrile acrylic-acid esters.
Coatings from aqueous dispersions of polyvinyl acetate have a high light permanence.
A polymer coating for single- and multicolour offprints, which possesses a mechanical
strength, has been developed.
There are stable and low-temperature-resistance aqueous dispersions of polymers. The
stability of the dispersions at a temperature of 15C for six months is achieved by using
a mixture of water and (ethyl, methyl) alcohol at weight ratios of 190:10100:100 as an
emulsion medium.
It is proposed to introduce synthetic (acryl, butadiene styrene, polyvinyl acetate) resins
into dispersions of epoxy esters to produce stable dispersions. A dispersion possessing both
a stability and low-temperature resistance was produced. The patent literature also recommends stable and low-temperature-resistant dispersions consisting of a homogeneous polymer or copolymer (e.g., ethylene and alkylacrylate, in the hydrocarbon chain of which
2.525% of carbon atoms are substituted by carboxyl, carboxylate or carbamyl.
Viscosity is of great significance in application of dispersions to paper. It has been
found that at the same dry residue a coarse dispersion of polyvinyl acetate has a viscosity
of 100 ps; a fine dispersion, several poise. It is proposed to regulate the viscosity of the dispersion of vinyl resins with crotonic acid. For this purpose, crotonic acid is added to the
dispersion of vinyl acetate, and copolymerization is carried out. By changing pH of the copolymer obtained, the viscosity of the dispersion is regulated within the required limits.
The dependence of viscosity and temperature has been studied; the viscosity of a polyvinyl acetate dispersion with particle size of 0.22.0 m was found to decrease with its temperature increasing.
Divinyl styrene latexes are used as coatings for paper to increase its printing properties
and the quality of typographic and offset printing; herewith, the resistance of the offprint to
abrasion in dry and moist state increases.
Divinyl styrene latex SKE-30, modified by an aqueous solution of polyvinyl alcohol,
is used to produce special lacquer-and-paint materials for the printing industry. Special
primers for producing paper-based binder materials were developed on the basis of this
latex.
However, coatings from these latexes are characterized by low decorative properties.

CHAPTER 4

141

A latex based on the copolymer of acrylate with vinylidene chloride Rhoplex A-9
is widely used for coatings on paper for packaging materials. This latex is colourless, preserves the flexibility of paper, causes no sticking, yields well to dyeing, but its film is not
light-permanent. Copolymers of vinyl chloride and vinylidene chloride are used for finishing packaging materials, paper and paperboard.
A possibility of using latexes manufactured by Russian industries for finishing printed
materials has been studied.
With this in mind, a large set of fine dispersions of polyvinyl acetate,
...

CH2

CH

...

OCOCH3

obtained under diverse conditions of synthesis (Table 4.1) and differing by their molecular
masses (Table 4.2), was synthesized in the presence of various emulsifiers (Table 4.3), with
introduction of phenol-formaldehyde resins. Analysis of the data presented in the tables
shows that PVA dispersions synthesized under various conditions yield no coatings with
the required set of mechanical and decorative properties. Regulation of the molecular mass
of polymer and the nature of emulsifier (Tables 4.2 and 4.3) failed to improve the decorative
properties of coatings. Modification of the PVA dispersion by phenol-formaldehyde resin
improves the decorative properties, but leads to a sharp increase of brittleness of the film
and to light nonpermanence.
Table 4.1
Type of latex

Dry residue, %

Fine-particle
polyvinyl acetate
(PVA) dispersion

48
49
47.8
48.7
49.0
48.5
47.9
49.2

Characteristics of dispersion and quality


of coating on offset imprint
Slightly sticky, light nonpermanent; grains in the
coating
nonsticky; good gloss but light nonpermanent
mat nonsticky film
low gloss; dispersion does not wet saturated areas
of offprints
dispersion soaks into the offprint without forming
a glossy coating even after two layers of coat
high gloss, coating non-sticky; dispersion unstable
(coagulates on day 3)
high gloss, coating non-sticky; dispersion unstable
(coagulates on day 3)
high gloss, coating non-sticky; dispersion unstable
(coagulates on day 3)

Table 4.2
Type of
latex

Dry residue,
%

Emulsifier

Fine-particle
PVA

48.7

OP-7

49.1

OP-10 with 0.2%


sulfanol addition

Characteristics of coating on offset imprint


no gloss; dispersion does not moisten black
ink
no glossy film is formed; dispersion does not
moisten saturated areas of offprint

142

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Table 4.2 (continued)


Type of
latex

Dry residue,
%

Emulsifier

49.5

OP-10

48.3

technical-grade
proxanol 228
16% proxanol
alphanol 12

48.5
47.9

Characteristics of coating on offset imprint


cast film is lusterless; dispersion does not
moisten black ink
cast film is lusterless; dispersion does not
moisten black ink
no film is formed
film is lusterless but non-sticky

Note: PVA, polyvinyl acetate dispersion; alphanol and sulfanol, anionogenic preparations; OP-8,
OP-10 and proxanol, nonionogenic preparations.

According to the data of patents, PVA dispersions have found wide use owing to their
relatively low cost.
Their major drawback is that at a normal temperature they are incapable of forming a
continuous film and, thus, need plasticizers to be added. Due to the volatility and migration
of plasticizers, the film is rapidly aged and becomes brittle. Besides, vinyl acetate ester is
apt to saponify. By introducing various additives, we succeeded in obtaining a composition
for finishing printed products; however, its use on the existing equipment is associated with
a number of technological difficulties.
To avoid introducing a plasticizer into the ready polyvinyl-acetate dispersion, a method of internal plasticization was used, namely, fabrication of copolymers of vinyl acetate
with other monomers (esters of unsaturated acids maleic, fumaric; esters of acrylic acid).
Table 4.3
Type of latex
Fine-particle PVA

Dry residue,
%

Molecular mass

43.7

96.600

45.6
47.3
45.2
48.3

79.700
67.900
53.300
90.600

43.7
44.3

Specimen of aqueous
dispersion from
Germany

non-sticky, with good gloss; dispersion


does not moisten black ink
dispersion coagulates on day 3
low gloss
no gloss at all; dispersion unstable
dispersion coagulates on day 2

hydrocarbon: H2O Monomer


ratio
dosage

Fine-particle PVA
with different
proportions of
monomer

Fine-particle PVA

Characteristics of coating
on offset imprint

2:3
1:1

with addition of water-soluble


phenol-formaldehyde resin

1/20
1/10

cast film has high gloss


but is very brittle

cast film is lusterless

rigidity of film increases and


non-light-resistance appears; in time,
introduction of resin causes coagulation of
dispersion
forms nonsticky coating, with high gloss;
cast film grows turbid in the light (on day
3); opacity increases in time

CHAPTER 4

143

Copolymers of vinyl acetate (VA) with ethylene grafted in several cases with acrylamide were tested. Aqueous solutions of solvars with various ratios of the hydroxyl and acetate groups, and dispersions of copolymers of polyvinyl alcohol with acrylonitrile and
acrylic acid (Table 4.4) form coatings with poor decorative properties. The decrease of the
number of acetate groups in solvar increases the gloss, but the adhesion of coatings becomes
worse in this case.
Table 4.4
Type of latex

PA copolymer : AAN

Ratio of
Dry Content of
components residue, acetate
%
groups, %
64:36

Latex rapidly soaks to form a


low-gloss film

PA:PVA (solvar)

PA copolymer : AA

VA copolymer : DAC

Characteristics of coatings
on offset imprint

21
18.2
9
Content of AA
7.6%
38%
25%

10.5
7.4
8.4

96:4
94:6
90:10
88:12

47.5
46.7
35.8
42.3

Gloss increases with decrease of


acetate groups, viscosity of solutions
increases
Coating has no gloss; viscosity of latex
increases with percentage of AA,
causing warpage of imprint
Cast films are yellow and
nontransparent; latexes are unstable
(peel off with time)

emulsion N-542

Film light-nonpermanent; gloss is


high after two coatings; lacquer film
can be calendered

NC with different
degrees of branching

Initial suspensions are very viscous;


when diluted, soak into imprint
without forming a glossy film

Note: PA, polyvinyl alcohol; AAN, acetic acid nitride; PVA, polyvinyl acetate; AA, acrylic acid;
VA, vinyl acetate; DAC, diallyl cyanamide; NC, nitrocellulose.

According to the literature data, at a certain ratio of components the copolymer of vinyl
acetate with ethylene has a higher strength and elasticity as compared with high-pressure
polyethylene; is resistant to cracking, action of ultraviolet rays; has good adhesion properties; is resistant to alcohols, glycols, organic acids and is used in a paper-finishing composition. The copolymer of vinyl acetate, ethylene and triallyl cyanurate is used to form a
smooth glossy coating on paper and paperboard.
Coatings with unsatisfactory decorative properties also form dispersions of vinyl acetate with diallyl cyanamide. Coatings from the emulsion based on nitrocellulose are distinguished with a low light permanence.
Aqueous dispersions based on copolymers of vinyl acetate with ethylene, grafted in
several cases with acrylamide, and introduced polymethyl siloxane (Table 4.5), as well as
copolymers of divinyl with methacrylic acid or methacrylamide fabricated at the S.V. Lebedev All-Russian Institute of Synthetic Rubber were tested as film formers for finishing

144

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

printed products. As seen, coatings based on these dispersions have poor decorative properties and low strength.
Table 4.5
Type of aqueous
dispersion

Colloidal characteristic Surface Characteristic of


tension,
free film
dyn/cm
dry pH ratio of
elong- tensile
residue,
components
ation, % strength,
%
MPa

VA copolymer:ET

49
49

3.9
3.9

VA copolymer:
ET:AA

47.4

80:15
82:12

Characteristic of
coating on offset
imprint

900
500

0.079
0.10

Very sticky
Very sticky

3.5 80.5:17:2.5

47.1

500

0.42

48.2
47.8

3.4
3.6

43
41.7

570
550

1.5
2.4

Coating is sticky,
dispersion does not wet
saturated areas
of imprint
Ditto
Ditto

VA copolymer:ET
with addition of
PMS-200

57.7

5.3 80:20 and


10%

39.3

550

2.7

Sticky due to residual


monomer (6.5%)

VA:ET with
addition of SiO2

44.3

5.5 90:10 and


20%

39

400

6.9

copolymer
DMMA-65-1GP
DMMA-65(60)-2

43.0

8.5

42.0

8.3

Grains in dispersion
make coating rough,
latex does not wet black
ink
Gloss not high; latex
does not wet black ink
Gloss not high; total
wetting of black ink

82:17:1
79:20:1

Note: VA, vinyl acetate; ET, ethylene; AA, acrylamide; PMS, polymethyl siloxane; DMMA-65-1GP,
divinyl and methacrylic acid; DMMA-65(60)-2, divinyl and methacrylamide.

As shown by the preliminary selection of dispersions and analysis of Western literature, acrylic dispersions of polymers proved to be the most promising for finishing coatings.
Acrylates begin to exhibit a film-forming ability almost at 0C; what is more, the produced
films are distinguished with a sufficient mechanical strength, as well as a high light and atmospheric resistance. A characteristic property of polyalkylacrylate films is their high
gloss, resistance to the action of UV light and molds.
Good results using these dispersions for finishing reel paper suggest that there is a tendency to use aqueous dispersions of polymers for finishing printed packaging material.
The employment of aqueous dispersions of polymers requires special equipment for
their application, development of special process regimes and method of drying polymer
coatings. These important issues are being dealt with for several years now by many advanced companies in developed countries.
Dispersions based on triple copolymers of ethylacrylate, nitrile acrylate, -m-styrene
with various ratios of the components were obtained (Table 4.6), as well as copolymers
based on ethylacrylate, nitrile acrylate, -m-styrene and 2-ethyl hexyl acrylate. It is seen

CHAPTER 4

145

that coatings based on these copolymers have poor gloss and do not wet the saturated regions of offprints.
Table 4.6
Ratio of components

Colloidal characteristic of Condition of


latex
synthesis
dry residue, sp
%

Characteristic of coating

pH

EA:NAC:-m-styrene
75:20:5

37.5

2.6

EA:NAC:-m-styrene
75:20:5
EA: 2-EHA: NAC:
-m-styrene 50:25:20:5
EA:NAC:-m-styrene
65:20:15
EA:NAC:-m-styrene
80:5:15

37. 5

2.0

37.6

3.4

3.45 Emulsifier was Coating has a pungent smell,


fed batchwise bad gloss; latex does not
moisten greasy areas of imprint
3.65 Emulsifier was Ditto
batched
4.7 Ditto
Ditto

38.1

1.9

3.6

Ditto

37.6

1.9

2.7

Emulsifier was
fed batchwise Ditto

Ditto

Note: EA, ethyl acrylate; NAC, nitrile acrylate; 2-EHA, 2-ethyl hexyl acrylate.

Thus, latexes produced by home industries and specially synthesized with the view of
using them for finishing printed products, do not form coatings satisfying the required set
of decorative and physicomechanical properties. Coatings based on these systems, as is
seen from the presented data, are sticky, with low gloss; they crack and have a smell.

4.3

The formation mechanism, structure and properties of finishing


packaging materials from aqueous dispersions

The mechanism of forming coatings from aqueous dispersions of polymers has not been
sufficiently studied until now. Most works in this field deal with the synthesis of latexes
and the development of the technological bases of their use. The reason for this is that the
processes of film formation from latexes have been studied using the methods, which do
not make it possible to investigate the kinetics of the process and the character of structural
transformations at particular stages of film formation. Methods of studying the kinetics of
moisture removing and electrical-conductivity changes were the most widespread. These
methods are not sensitive to the changes of the properties of films after moisture is removed.
It is known that the process of coatings and films formation does not end at this stage and
is accompanied by further structural transformations after the removal of moisture.
Most works analysing the film-formation mechanism consider latexes as typical
colloidal systems without taking into account the polymer specifics of the disperse-phase
material. It is assumed that certain conditions different from those in production of films
from polymer solutions should be met to produce a continuous film from latex.
This is due to the fact that a polymer in latex is distributed not in the form of more or
less associated molecules, but in the form of particles containing sometimes tens of
thousands of macromolecules.

146

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

1-3

r
F2

F
1-3

Figure 4.1 An action pattern of forces contributing to the coalescence of latex particles.

Film formation from latexes is associated with the consideration of factors, which
affect the rate of deformation and coalescence of latex particles, such as surface tension,
capillary forces, diffusion, nature of polar groups, film formation temperature, etc.
In a number of works, the driving force of film formation is taken to be the surface
tension at the polymerair interface, which tends to reduce the surface of the polymer
phase.
It is assumed that after the evaporation of water latex particles flow in under the
action of the surface tension force, which depends on angle (Fig. 4.1), the value of which
is determined from the Frenkel equation

3 13 t
= ---------------,
2 r

where 13 is the surface tension at the polymerair interface, t is the contact time of particles, is the viscosity of polymer and r is the radius of a polymer particle.
It is assumed that the force of interaction between latex particles depends on their size;
herewith, it is not taken into account that particles themselves can have diverse shapes.
In works by Brown, of crucial importance in the film formation process are capillary
forces, which act against forces of electrostatic repulsion and forces of strain (deformation)
resistance identified with polymers elasticity modulus. At a certain value of the modulus,
particles are not able to get deformed, so no film is produced.
The capillary forces depend on the surface tension at the polymerair interface and
the capillary radius rc
2
F = --------1- .
rc
Assuming that aqueous streaks between latex particles have the form of a cylinder
(Fig. 4.2a), we can determine the radius of a capillary
r ( 1 cos 30 )
r c = ---------------------------------- ,
cos 30
where r is the radius of a latex particle.

CHAPTER 4

rc

147

FH
Fn

30
r

rc

Figure 4.2 An initiation pattern of capillary forces during the drying of latex: a, initiation pattern of
capillary forces; b, resolution pattern of capillary forces.

According to Brown, the film-formation process occurs when


F1 + F2 + F3 + F4 > F5 + F6 ,
where F1 are the capillary pressure forces, F2 is the force depending on the surface tension
at the polymerwater interface, F3 are the forces of molecular interaction, F4 the force of
gravity, F5 is the resistance to strain, F6 the force of electrostatic repulsion.
At the same time, it has been found that the size of particles, on which the capillary
pressure depends, has no effect on the film formation process, and the last stage of film formation from latex can be determined by its polarity or autoadhesion.
Film formation can have the diffusion-osmotic mechanism. In this case, it is assumed
that water is fed to the surface not only through capillaries, but also via latex particles themselves, proceeding from the assumption that for real latexes the surface tension at the water
phaseair interface is greater than 30 dyn/cm and the wetting angle is greater than 0.
Therefore, a force applied to the wall of a capillary can be resolved into two components
(Fig. 4.2b): normal, Fn = 2 rc 23cos and tangential, FH = 2 rc 23sin , where Fn is
the compressing force directed inside the specimen and FH is the force directed along the
surface and tending to close the openings of the capillary. For synthetic latexes, FH > Fn.
The polymer film formed on the surface of drying latex is permeable for water vapours,
not impermeable for water itself; because of this, an osmotic pressure emerges, which is
directed inside the film and is compacting its structure. It is concluded that the main source
of energy in film formation is ambient heat transformed into effective work in the evaporation of water via latex particles. The action of capillary forces has to do with faster drying
of latex films if the polymer is in a rubberlike state as compared with the polymer in a viscoelastic state.
The main criterion of film formation in a number of cases is taken to be the minimum
film formation temperature (MFFT), i.e., the temperature above which globules of thermoplastic polymer are capable of deformation to form a continuous film. MFFT is an essential
characteristic of the film-forming latex. It is assumed to correspond to the temperature of
the transition from the glassy to the rubberlike state. However, it has been shown that formation of films can occur at temperatures lower than the glass transition temperature of a
polymer; as the result of the contact of latex particles one with another, there will be the

148

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

interpenetration of macromolecular segments on their surface, possessing a significant freedom of rotation. Therefore, it is suggested that the temperature of film formation should be
the function of the ratio of the surface to the volume of the polymer phase. On the other
hand, one of the works showed not only the feasibility of film formation but also its kinetics
to depend on the physical state of the polymer.
Film formation depends not only on the colloidal and rheological properties of latex
but also on the chemical composition of the polymer.
Studies of the effect of polymer polarity on the rate of film formation by the example
of latexes of various copolymers of ethylacrylate have shown that the rate increases with
the polarity of the polymer going up.
An essential drawback of those works is that they fail to take into account the crucial
role of structural transformations during the formation of the properties of latex films. This
was first noted in the works by S.S. Voyutsky and coworkers, who considered formation of
films from latexes as a multistage process. Of crucial significance is the last stage of film
formation associated with the redistribution of emulsifier, the deformation and coalescence
of latex particles. The redistribution of emulsifier and its dissolution in the polymer can be
contributed to by the diffusion of macromolecules similar to how it takes place in the formation of films from other systems. Even at a very low content of emulsifier in the latex
film, its water absorption was shown to depend on the structure of the latter. Water absorption of acrylate latexes synthesized at the same consumption of the initiator and emulsifier
decreases with the increase of the elasticity modulus of the polymer and an increase of its
molecular mass. This can be explained by the increase of the intermolecular interaction, at
which the number of holes, formed in the thermal motion of polymer macromolecules
and responsible for water absorption, decreases. A similar dependence of water absorption
of latex films from polyvinyl acetate and its copolymers with butyl acrylate on polymers
deformation resistance was obtained.
In all these works, latex particles were considered as a ball of irregularly intertwined
macromolecules kept together by the forces of intermolecular interaction.
Studies of the fine structure of latex coatings and its effect on the properties of the latter
have not been given due attention. Studies of latex particles were mainly reduced to the revelation of their size; and studies of structures of films, to observations of replicas from their
surfaces in an electronic microscope.
We investigated the structure of latex particles and its effect on the structure and properties of coatings by the example of commercial latexes. For electron-microscopy studies
of the fine structure of latex particles, we used the method of oxygen etching.
As a result of these studies, we found latex particles to be complex supramolecular formations consisting of simpler structural elements. The size and morphology of the structures occurring in latex particles depends on the chemical composition of the polymer, the
nature of the functional groups, the colloidalchemical nature of latex.
To study the mechanism of formation of latex coatings, in these works we used new
methods enabling us to investigate the properties of latex coatings at various stages of film
formation and to assess the emerging internal stresses in the coatings, which cause spontaneous curling and warping of the materials. A relationship between the structure and properties of latex coatings was established.
Internal stresses emerging in the formation of coatings are determined by the rate of
inhibition of the relaxation processes, which depends on the architecture of molecules and
the character of supramolecular structures they form.
The significance of the relaxation processes in drying was first noted in the works by

CHAPTER 4

149

Academician A.V. Lykov, who proposed methods for the calculation of internal stresses,
with account for the fields of temperature and moisture content, and deduced a dimensionless criterion of crack formation depending on the operational parameters of drying.
V.A. Kargin et al., G.L. Slonimsky, P.I. Zubov and T.I. Sogolova investigated the nature of the relaxation processes in polymers and their role in the formation of coatings; this
process was shown to be accompanied by the emergence of local links between the most
active groups of polymer molecules. The number and nature of these links, as well as the
conformation of macromolecules, render an effect on the rate of the relaxation processes
and the value of internal stresses.
A peculiar feature of the formation of latex coatings is the nonmonotonic change of
internal stresses in the film-forming process. First they increase and reach a maximum after
the removal of moisture, and then relax to a constant value.
Studies of the structure of the initial dispersions and coatings on their basis revealed
that after moisture removal the coatings preserved latex particles whose diameter, depending on the nature of polymer, changed little within the limits of 0.15 up to 0.17 m. With
this in mind, special attention was paid to studies of the structure of latex particles; it was
shown that they were complex supramolecular formations consisting of simpler and finer
supramolecular structures.
A direct relationship was established between the structure of latex particles and the
rate of the relaxation processes; the relaxation processes are completed the fastest in coatings with the least number of globules (equal to 50, of about 30 nm in diameter) in a latex
particle. As the number of globules in a latex particle increased by two orders of magnitude
and their diameter decreased to 910 nm, the relaxation processes were sharply slowed
down and were completed in 30 days of formation.
Studies of the supramolecular structure at particular stages of formation of latex coatings have established that the removal of moisture was accompanied by the preservation of
latex particles with the emergence of local links between them and structural elements that
form them.
The subsequent relaxation processes are associated with the breakdown of latex particles and the rearrangement of their constitutive structural elements.
Thus, formation of latex coatings is not completed after moisture removal and consists
of two stages. The first stage is associated with the increment of internal stresses as the result of establishing local links between latex particles and their constituent structural elements during the removal of moisture from the system.
The second, longer stage is to break down latex particles and to rearrange their constitutive structural elements, which leads to the relaxation of internal stresses.
The methods of measuring the kinetics of increment and relaxation of internal stresses
and measuring the thermal and physical properties of coatings, proposed in these works, are
of significant interest for coating formation studies and of great practical importance.
In contrast with the methods of studies of other mechanical and electrical parameters,
they make it possible to follow the complete process of forming films on the support on one
specimen and to assess the change of the properties of latex coatings after moisture removal.
The earlier used methods of studying the film-formation kinetics by the change of
moisture and electrical resistance failed to detect structural transformations in latex coatings after removal of moisture from them.
Using this method for studies of internal stresses, it has been shown that the character
of the kinetic curves of the increment and relaxation of internal stresses does not depend on
the nature of the support, which has a significant effect on the value of internal stresses.

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Ways to decrease internal stresses during the formation of latex coatings were proposed by regulating the character of structural transformations and by forming an ordered
supramolecular fibrillar-type structure in latexes and coatings on their basis, using modified
additives and changing the colloidalchemical nature.
This made it possible not only to reduce internal stresses in the system, but also to considerably decrease their formation period, to sharply increase adhesion and strength of latex
films.
Studies of the effect of structural transformations in latex films on the decorative properties of coatings have not been given due attention. This complicates the choice of latex
systems for finishing packaging and printed products and does not make it possible to define
the main requirements to the structure and chemical composition of a latex formulation,
which provide for the required set of mechanical and decorative properties of coatings.
The process of forming coatings from aqueous dispersions of polymers on fibrous
bases of the type of paper and printed products has been little studied. The effect of the
chemical composition of the dispersion, the nature and concentration of polar groups, the
colloidalchemical nature of latex has not been investigated.
The most promising class of film formers for finishing printed products are aqueous
dispersions of polymers.
To develop aqueous dispersions of polymers used for finishing printed products, the
effect of various physicochemical factors on the decorative properties of the coatings, such
as the structure of latex particles and coatings, the nature of the functional groups and their
distribution on the surface of latex particles, the colloidalchemical nature of latex has been
studied.
These studies made it possible to develop the physicochemical bases of the synthesis
of latexes forming the coatings with high decorative and protective properties.

4.4

Characteristics of finishing packaging materials

The mechanism of film formation from aqueous dispersions of polymers has not been studied sufficiently. The earlier used methods of studying the kinetics of moisture removal, the
changes of electrical conductivity; of plotting the thermomechanical curves, do not make it
possible to investigate completely the kinetics of the process and the character of structural
transformations occurring as the result of incompletion of the relaxation processes.
To study the process of coating formation from latexes, we investigated the kinetics
of the increment and relaxation of internal stresses. The internal stresses were determined
by the polarization-optical method broadly used in various industries.
The peculiar feature of the method we used is that stresses are assessed by the value
of the birefringence in the support at the interface with the film. This excludes the need for
measuring additional physicomechanical characteristics for calculating internal stresses,
which change during the formation and ageing of the coatings.
Glass isotropic prisms in the form of parallelepipeds, 102030 mm in size, which are
an optically sensitive material with a linear dependence between voltages and birefringences within a broad range of voltages and temperatures were used as a support. The error of
the method does not exceed 510%. The value of the method is also that, along with internal
stresses, it determines adhesion of coatings, which is assessed by the maximum critical
stresses causing the spontaneous delamination of the film from the support at a certain
thickness of the coatings. The critical stresses were developed by forming an epoxy coating
on the latex coating obtained on a glass support. The optical schematic of the recording

CHAPTER 4

10
11

Figure 4.3

151

+
Rcr

The electro-optical schematic of the instrument.

instrument is given in Fig. 4.3.


A beam of light from incandescent lamp 1 (170 W, 17 V) passes through condenser 2
and is fed via polarizer 3 to measured specimen 4. Through slit 5 (0.50.5 mm in size) and
object lens 6 the light comes to analyzer 7 crossed with polarizer 3 and goes to measuring
photocell 8. Compensation photocell 9 is connected in parallel to the measuring photocell.
A light beam from source 11, which has a system of diaphragms and neutral wedge 10, is
incident on the compensation photocell. The compensation part of the circuit, connected toward the measuring photocell, serves for the exact zero point adjustment in the electric circuit. Internal stresses in various planes are measured by automatic displacement of the table
with the specimen at a rate of 4 mm/min.
Studies of stresses by the optical method during the formation of coatings on various
supports can be done by preliminary pasting or depositing a support in the form of a layer
10 to 100 m thick on the surface of the glass prism, followed by the application of a polymer coating to this support. Various supports were pasted by a glue based on epoxy resin
ED-5 applied as a thin layer 36 m. Using this method of pasting, there were practically
no internal stresses in the glass prism before the application of coatings.
Using the optical method, we studied the effect of various factors on the value and
increment/relaxation kinetics of internal stresses, such as the chemical composition of film
formers, the colloidalchemical nature of latex, the nature and polarity of the functional
groups, the effect of the nature and structure of the support, the formation conditions and
methods of drying the coatings.
The kinetics of drying latex coatings was studied by the weight method. The same
amounts of latex of a known concentration (in our experiments, it was 0.010.015 g at a
latex concentration of about 50%) were applied to glass plates of 1020 mm. The glass
plates were periodically weighed at room conditions (at a temperature of 20C and relative
humidity) at certain time intervals on an analytical balance until a constant weight was
reached.
Penetration of polymer into the fibrous support in the process of drying of the coatings
was determined by the fluorescence of transverse sections of papers (offprints) with a coating in an ML-2 ultraviolet microscope. The source of light is a DPSh-250 mercury lamp,
which gives an intensive radiation in the blue-violet region of the spectrum up to the wavelength of 340 nm. The operation of the instrument is based on the use of the fluorescence
of belofors, which occurs under the action of beams of a certain spectral composition. The

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

6
5
2

to pressure gauge

4
cooling

to pump
Figure 4.4

light of the fluorescence has a longer wavelength than the light exciting the fluorescence.
Belofors having an affinity to the polymer (Belofor SNPA) were used as optically bleaching
substances. A minor amount of belofor (0.0054 g per 50 g latex) was introduced into the
initial dispersion, and then the dispersion was evenly applied to the supports by means of a
spreading knife; the weight of the applied dispersion was controlled.
The supramolecular structure of latex coatings was studied using an electron microscope by means of the method of carbon replicas. In some cases, the specimens were subjected to oxygen etching to reveal the structure more clearly.
Activation of oxygen was performed in an electromagnetic high-frequency field. The
advantage of this method of etching is that the substance is treated not for a long time and
evenly without increasing the temperature or increasing it comparatively little within the
limits of 24C.
The specimen was etched in a tube presented schematically in Fig. 4.4.
After specimen 2 is introduced through the side tap, a vacuum of up to 10 3 mm Hg
is created and an oxygen flow at a pressure of 34 10 2 mm Hg is set by means of a needle
valve. Then a discharge is carried out. The etching time was adjusted experimentally to
810 min.
Oxygen etching contributes to a more pronounced revelation of the structure, without
changing its character, as the result of the elimination of a low-molecular-mass less ordered
structure.
Preparations were observed at an UEMB-100 electron microscope.
The molecular structure of the coatings, with account for the distribution of the polar
groups on the surface of latex particles and the formation of hydrogen bonds between them,
was studied by the method of IR spectroscopy. Formation of films from latexes was
performed on fluorite plates. IR spectra of the latex coatings were recorded by an UR-20
instrument.

CHAPTER 4

153

The size of latex particles was determined by the method of electron microscopy by
preparing preparations from very dilute dispersions at a concentration of 0.001%; these data
were simultaneously compared with those of the diameter of particles obtained by means
of an FEKN-57 nephelometer.
The macrostructure of the initial papers was examined in reflected light on an MIM-7
microscope. Specimens of papers studied were preliminarily contrasted.
The microstucture of the initial papers was examined in an UEMB-100 electron
microscope. Specimens were obtained by dispersing papers by means of an UZDN-1 ultrasonic disperser at a frequency of 15 kHz for 30 sec.
The rheological properties of latexes, depending on their composition and colloidal
chemical nature were studied on a viscosimeter with Shvedov-type coaxial cylinders and
were assessed by the character of the viscosityshearing stress curves.
Stressstrain characteristics were recorded at room temperature by a Polyani instrument to characterize the mechanical properties of films. Specimens for tests were cut as
rectangles 455 mm in size from the most even-thickness part of a film. The area of the
working part was 105 mm2; the loading rate, 610 mm/min. The mean values of the
stress-strain characteristics were obtained from 910 parallel determinations.
The thermomechanical properties of polymers were assessed by the change of strain
on temperature. The thermomechanical curves were registered on a Kargin balance at a constant load and heating rate.
Factors affecting the quality of lacquering printed offprints at various types of papers
were studied. The method of determining the extent of lacquering is based on the assessment of the rate of lacquer penetration into the support and depends on the absorption properties of the support.
To assess the extent of lacquering of saturated regions of an offprint with dispersions
studied, we measured the contact angle of wetting at the offprint surface /drop of
dispersion/air interface and determined the wetting as a function of time (rate of absorption)
by the drop contour projection method.
The character of the kinetic curves of wetting is similar, so the data of measurements
are summed in the table.
The gloss of the coating is one of the major decorative parameters of the coating quality. Objective methods of measuring the gloss have been developed. The Fairchild glossmeter is the most advanced, as it enables measuring the gloss of paper continuously by
means of a comparative method, can be used at a high temperature, humidity in the presence
of corroding chemicals and vapour, has a number of design advantages. The gloss of coatings under study was measured by a glossmeter, was assessed with respect to black glass
and was expressed in percent.
Cohesion of lacquered offprints was determined by the method proposed for binding
fabrics. The method consists in determining the force of cohesion emerging as the result of
the contact of the face surfaces of lacquered offprints at a certain temperature, pressure and
time. Specimens were prepared as follows. Straps of lacquered products of 3050 mm in
size were preliminarily held at a 100% relative humidity on an exciccator mesh (with the
face part up) for 30 min, them placed into a press mold heated up to 302C, were subjected
to compression at a pressure of 2005 kgf for 1 min, removed from the press mold and put
between glass plates under a load of 1 kg for 24 h. Then the specimens were subjected to a
load, required for a shift of the surfaces, in a tensile tester.
The force of cohesion (B) in kg/cm2 was determined by the formula:

154

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

P
B = --- ,
S
where P is the load at the shift of the surfaces in kg and S is the contact area of the specimens
in cm2 (of 57 parallel tests to an accuracy of up to 0.1).
The lacquer film on an offprint should have an abrasion resistance and elasticity. The
resistance of a coating to abrasion can be defined by the length of a path, in passing which
the coating is being broken, and be characterized by the number of turns of a prism before
the appearance of the paper base. Specimens studied are fixed on to the prisms; the specimens are in contact with a closed band made from the fabric used as a counterbody in abrasion. The fabric band is cut of the same size as the base, is pulled tight by a load of 3 kg,
and then the cross with the prisms is rotated at a speed of 60 revolutions per minute. The
mean arithmetic of six parallel determinations was taken as the abrasion result.
Elasticity of the coating was assessed by the number of double bends in tests on an
MIDP-1 instrument used in printing industry. The method consists in determining the number of double bends to an angle of 150 to each side from the vertical position of the material
being under tension, up to the emergence of cracks on the film coating or the break of the
specimen.
Durability of coatings on paper is assessed not only by the values of internal stresses,
but also by its resistance to ultraviolet radiation. The light permanence of coatings was estimated by a faster method from the change of the colour of the specimens as compared with
the reference methods under the action of ultraviolet radiation of a PRK-4 lamp. A correlation between the data obtained by the faster method and under natural testing conditions
was established.

4.5

Aqueous dispersions of polymers for finishing coatings, offset papers


and inks

To enable the use of aqueous dispersions of polymers for finishing printing products, the
mechanism of forming coatings from latexes was studied with the aim to establish relations
between the chemical composition of the dispersion, structure of latex particles and decorative properties of coatings.
Latexes manufactured by home industry were tested. However, the coating produced
from these compositions on offprints does not conform to the requirements imposed on the
quality of lacquered products. These were systems based on copolymers of vinyl acetate
and other monomers (coatings possess a high tackiness, low gloss; and dispersions themselves, unstable properties). The major characteristics of tested latexes are given in the table. Taking account of this, acrylic dispersions both commercially manufactured and
specially synthesized were chosen as promising film formers.
Of commercial dispersions, the latexes tested were polyalkyl acrylates based on acrylCH3
ic acid CH2
R ,
namely:

CH
COOR

and methacrylic acid CH2

and their esters, where R H1CH3

COOR

copolymer of butyl acrylate with meth- or ethacrylate and MAA

CHAPTER 4

CH3

MBM-5s

...

CH2

...

CH

CH2

COOC4H9

CH3
...

155

CH2

COOCH3

...

COOH

copolymer of butyl acrylate with methyl acrylate and MAA


CH3

MBM-3

...

CH2

CH

...

CH2

COOC4H9

...

CH

CH2

...

COOH

COOCH3

copolymer of methyl acrylate with vinyl acetate and MAA


CH3

MVM-1.5s

...

CH2

CH

...

CH2

COOCH3

CH

...

CH2

OCOCH3

...

COOH

the composition and colloidal characteristic of which are given in the table.
Coatings from these latexes on offprints possess a tackiness and low gloss.
A dispersion based on polyalkyl acrylates, which forms coatings with high decorative
and physicomechanical properties, was developed. As the result of the studies, it was found
that latex BM-12, of the structure
CH3

CH3
...

CH2

CH

...

COOC4H9

CH2

...

COOC4H9

CH2

...

COOH

forms a glossy, nonsticky coating with high adhesion and physicomechanical properties.
This latex is produced in the presence of an emulsifier (sulfanol) and an initiator (ammonium persulfate, 0.15 parts by weight).
Dispersions of the BM-12 formulation with pH from 2.5 up to 8.4 were synthesized to
study the effect of the colloidalchemical nature of latex, namely, pH of the medium. These
latexes were produced by the method of hot neutralization by introducing various amounts
of ammonia (Table 4.12) into the latex.
Latexes with various polar groups carboxylic (COOH), amide (CONH2) and
nitrile (CN) are obtained by the method of emulsion polarization with equal amounts of
the same emulsifier (sulfanol), with the other similar conditions observed, by introducing
12 wt.% monomers with various functional groups: methacrylic acid, methacrylic-acid
amide and a mixture of methacrylic acid and acrylic-acid nitrile (Table 4.13).
A peculiar feature of investigated latexes with various amounts of methacrylic acid
from 2 up to 15 wt.% is that it was introduced as a monomer in emulsion polarization performed by a semicontinuous method with the triple dosage of monomer and emulsifier. The
colloidal characteristic of synthesized latexes is given in the table.
To study the formation process of polymer coatings on offset papers and offprints, the
following were chosen: plain offset paper and an offprint obtained under production

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

conditions by the offset method during the application of inks of the 2513 series. Papers for
different methods of printing differ mainly by their moisture resistance (degree of sizing),
smoothness, elasto-plastic properties, absorptivity (porosity and capillarity) and strength of
the surface. These are the essential printing properties of a paper, on which its behaviour in
the printing process depends.
A number of requirements are imposed on offset paper; these are stipulated by the specific features of offset printing, when an ink image is transferred from the offset plate to
paper by means of the offset rubber cylinder, and the offset plate is systematically moistened with water in the process of printing.
Therefore, offset paper should be sufficiently moisture-resistant, i.e., well sized with
rosin size, and sometimes additionally with starch. Highest quality offset paper, e.g., map
paper, is obtained by using melamine-aldehyde resin in combination with wood rosin as
size. A high degree of sizing of offset paper (1.25 mm) is required, first, to avoid excessive
deformation of paper in its contact with the moistened offset cylinder and, second, so that
there is no decrease of strength of the surface of paper in moistening and an associated fluffing of paper by ink.
The elastic and plastic properties of offset paper are undesirable, as in printing they
cause ink squeezing on the offprint. For this reason, the content of filler in the offset paper
is always lower than in printing paper or in intaglio paper.
The absorptivity of offset paper can be limited, if the inks used are fixed by oxidative
polymerization or evaporation of a high-boiling solvent, especially in gas-flame drying of
offprints. However, when using inks fixed by selective absorption of the bonding adhesive,
the absorptivity of offset paper should be high, which is achieved by increasing the capillarity of the paper owing to the increased content of filler (more than 15%) and preservation
of porosity and capillarity of the paper in its fabrication on a paper-making machine. Besides, in offset printing some roughness of paper prevents ink scuffing.
The major types of plain papers, depending on their purpose, composition with respect
to fibre content and technical parameters, are produced as numbers 1, 2 and 3, which denote
certain compositions (Table 4.7).
Papers of each number are divided into several grades denoted by letters A, B, C and
D for the same composition, having slightly different degrees of smoothness, ash content
and bulk density.
Table 4.7 Composition of printing paper (in %).
Fibrous semi-finished products

Bleached sulfite cellulose, no less than


Unbleached sulfite cellulose, no less than
White woodpulp, no more than

Paper
No 1

No 2

No 3

100

50

50

35
65

Map paper is a high-grade offset paper intended for printing topographic, hydrographic and geographic maps. The requirements to map paper include those for offset paper
and some additional requirements due to the specific features of map production and conditions of map use. Map paper should have a high degree of whiteness (without any additional tint), the homogeneous smooth, closed-up surface, additional abrasion resistance,
resistance to moisture and atmospheric effects (rain, snow), minimal and even deformation

157

CHAPTER 4

in moisturing, minimal speckiness (specks of more than 15 mm are inadmissible), high light
permanence.
Map paper is fabricated from bleached sulfite cellulose and linen rag pulp (Table 4.8),
has a wood resinmelamine sizing of no less than 1.75 mm, i.e., much greater than common
offset papers.
Table 4.8 Composition of atlas paper.
Fibrous semi-finished products Grade A (hydrographic
and topographic)
Bleached linen rag pulp, no less
than
Bleached sulfite cellulose, no more
than

Grade B
(geographic)

Grade C
(geographic)

30

50

70

50

100

With this in mind, to study the formation mechanism of coatings from polyalkyl acrylate latexes, we chose different papers, whose properties are given in the table.
As ink sublayers, printing inks intended for offset printing were used.
When fabricating offset colour inks, account should be made of the offset printing process and, mainly, the character of the printing plate and regime of its moistening in printing.
Therefore, offset colour inks are usually fabricated on viscous and sticky bonding adhesives
from absolutely water-proof pigments (or lacquers).
Earlier, offset inks were produced predominantly on alkid and natural drying oils;
nowadays, on composition drying oils.
Composition drying oil is a mixture (composition) of specially selected resins, synthetic polymers, highly viscous drying oils, mineral or vegetable oils, and high-boiling organic solvents. To accelerate ink fixation, the formulation of inks is supplemented with a
siccative a catalyst of oxidative polymerization of the bonding adhesive.
The inks of the series used are the most advanced. The composition of the ink is
approximately as follows:
pigment
composition drying oil
thinner
siccative.
Depending on the colour of the ink, respective pigments are used:
Ink number
011
231
331
531

Ink colour

Pigment name

black
magenta
cyan
yellow

channel carbon black


ruby lacquer SK
heliogen blau LBGN
yellow clear 0

Offset inks of this series are fixed on paper due to the partial selective ink penetration
and oxidative polymerization of the bonding adhesive.
Polyalkyl acrylate dispersions were applied to dry offprints.
Conducted research in the field of printed-matter finishing enabled the major

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

conclusion that the finishing material should be chosen to match paper and inks. It is not by
chance that in the West acrylic dispersions are used in the paper-making process with the
aim to improve their printing properties; printing aqueous acrylic inks are being developed.

4.6

Properties of finishing coatings from aqueous dispersions of acrylic


polymers

Studies of the formation of coatings from industrial latexes have established that the structure of latex particles has a significant effect on the rate of relaxation processes, kinetics of
increment of internal stresses, adhesion and other physicomechanical properties of the
coatings.
It could be expected that the structure of latex particles, which depends on the chemical
composition of a polymer, the nature and concentration of polar groups, the colloidal
chemical nature of a latex, should also have a significant effect on the decorative properties
of the coatings, determining the quality of finish of printing products.
With account for this, we studied the effect of the chemical composition of polyalkyl
acrylates on the structure of latex particles and coatings, established the relationship
between the character of structural transformations in the formation of latex coatings, decorative and physicomechanical properties of the coatings.
For solving this problem, we studied the effect of the chemical composition of polyalkyl acrylates on the structure and properties of coatings, chose the composition forming
a coating with the required set of properties.
The latex coating formation process was studied by investigating the kinetics of increment and relaxation of internal stresses.
It follows from the analysis of the data on the kinetics of increment and relaxation of
internal stresses in the formation of coatings from latexes of acrylic copolymers of various
chemical composition (Table 4.9) that for coatings from latexes MBM-3, MBM-5s,
MVM-1.5s the internal stresses change nonmonotonically: first they increase and then relax. A specific feature of the hardening of coatings from latex BM-12 is associated with a
rapid increment of internal stresses in the initial stage of formation and their stability in the
subsequent formation of the coatings (Fig. 4.5).
Table 4.9 Characteristics of various latexes.
Synthesis
No

Latex
name

50 shopfloor
MBS-5s
278 shopfloor MBM-3
133-1
MVM-1.5s
112
BM-12
experimental

Ratio of components, wt. %

Colloidal characteristic
of latex

BA

MA

VA

dry
residue,
%

sp

pH

55
62

30

35
70

28.5

49.0
40
48.0
49.0

2.5
7.4
2.5
3.6

4.5
6.0
3.0
3.0

BMA MMA MAA

70

40

5
3
1.5
12

Note: BA, butyl acrylate; MA, methyl acrylate; VA, vinyl acetate; BMA, butyl methacrylate; MMA,
methyl methacrylate; MAA, methacrylic acid.

CHAPTER 4

159

b10, MPa

16
12
4
3
1
2

8
4

12

400

600

800

1000
, h

Figure 4.5 Kinetics of increment and relaxation of internal stresses in the formation of coatings
from latexes of various chemical compositions: 1, BM-12; 2, MBM-3; 3, MBM-5s; 4, MVM-1.5s.

u, %
100
80
60
40

20

1
2

10

, min

Figure 4.6 Kinetics of drying of coatings from latexes of various chemical compositions: 1,
BM-12; 2, MVM-1.5s; 3, MBM-3; 4, MBM-5s.

Analysis of the curves of drying of various-composition latexes indicates that the most
rapidly drying coatings are those from BM-12 and MVM-1.5s (Fig. 4.6). Comparison of
the kinetics of drying of the coatings with the kinetics of increment of internal stresses indicates that the most sharp inhibition of the relaxation processes is observed in the period
of the dropping rate of drying and is due to the formation of local physical links between
structural elements. Significant differences in the mechanism of formation of the coatings
from latexes of acrylic copolymers, differing by their chemical composition, are determined
by the specific features of the structure of latex particles and the distribution of polar groups
on their surface. These factors determine not only the mechanism of formation of the coatings from latexes, but also the properties of polymer dispersions.
Figure 4.7 presents a dependence of viscosity on shearing stress for dispersions of various chemical compositions. It is seen that dispersions from copolymers MBM-3 and
MBM-5s are weakly structured systems passing to a state of viscous flow at a comparatively
small shearing stress. The system of copolymer BM-12 is more structured and breaks down

160

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

, 10 Pa . s
24
20
12
8
4

3
2

2 4

40

80

120
160
P, 10 Pa

Figure 4.7 Dependence of viscosity on shearing stresses for latexes of various chemical compositions: 1, MBM-3; 2, MBM-5s; 3, BM-12.

at a shearing stress by an order of magnitude higher than BM-type latexes.


This is, evidently, due to the smaller size of latex particles in the BM-12 dispersion,
determined by the results of electron-microscopy studies (Table 4.10), and also by the concentration of a significant amount of polar groups on their surface. For this reason, coatings
from the dispersion of BM-12 are characterized by a considerably smaller formation time.
Table 4.10
Adhesion A,
Relative
Copolymer Particle size, Adhesiveness Gloss relative Strength p,
MPa
MPa
elongation ,
m
of coating, to black glass,
%
MPa
%
MBM-5s
MBM-3
MVM-1.5s
BM-12

0.175
0.225
0.22
0.14

sticky
very sticky
0.34
0.100.12

12
14
11
49

7
4.6
8.0
8.0

400
1500
500
90

1.8
1.6

4.0

IR spectra recorded for films from latexes of various chemical compositions have a
broad band in the region of 3300 cm 1, characteristic of a hydrogen bond, apparently forming as the result of intermolecular interaction of polar groups. The largest intensity of this
band is indicative of a larger concentration of hydrogen bonds in the system for a coating
from test latex BM-12 (Fig. 4.9).
Studies of the adhesion of latex coatings to glass by the value of ultimate critical stresses causing the spontaneous delamination of the film from the support have found that coatings from latex BM-12 are characterized by a greater adhesion of about 4 MPa. In coatings
from MBM-type latexes the relaxation processes determined by the disturbance of adhesion
interaction are observed at stresses of about 1.62 MPa (Table 4.10).
Figure 4.8 presents the stressstrain characteristics of coatings formed from latexes of
various copolymers. It is seen that films from latex MBM-3 are characterized by a very high

CHAPTER 4

80
p 10, MPa

161

60
2
40

20

40

80

120

400

800

1200 1600
, %

Figure 4.8 Stress strain characteristics of films formed from latexes of various chemical compositions: 1, BM-12; 2, MVM-1.5s; 3, MBM-5s; 4, MBM-3.

1 23 4
Transmission, %

3460
3300

2990
3600

3400 3200

3000 2800 2600 2400


cm1

Figure 4.9 Spectrogram for films from latexes of various chemical compositions: 1, MVM-1.5s; 2,
MBM-3; 3, MBM-5s; 4, BM-12.

relative breaking elongation and the smallest strength as compared with films from the other
systems studied. Introduction of methyl methacrylate considerably increases the strength
of the system and contributes to the decrease of relative elongation.
Films from latex MVM-1.5s become hazy in the process of deformation and change
their structure, which stipulates the complex character of the stressstrain dependence. The
physicomechanical properties of coatings from latexes of various chemical compositions
were compared with the process parameters characterizing the decorative properties of
coatings (Table 4.10). It is seen that coatings from latexes MBM-5s, MBM-3, MVM-1.5s
are distinguished by a high tackiness and low gloss.
Coatings from test latex BM-12 were found to have the best decorative properties.
The thermomechanical curves taken on a Korgin balance (Fig. 4.10) show that the

162

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

70
60
50
40
30

20
10
-10 0 +10

+30

+50

+70

+90

+110
T, C

Figure 4.10 Thermomechanical curves plotted for films from latexes: 1, MVM-1.5s; 2, BM-12.

copolymer MVM-1.5s has a low glass-transition temperature and passes into the rubberlike
state at a lower temperature as compared with copolymer BM-12.
Films from MBM latexes start to exhibit a plastic flow at a temperature of +10C.
Comparison of the kinetics of the formation of coatings with their process parameters
and physicomechanical properties indicates that the high tackiness of coatings from MBMand MVM-type latexes and low gloss are related to the instability of their properties in the
formation process, to the incompleteness of the structural transformations and the prolonged formation time.
The supramolecular structure of latex coatings was studied using the method of oxygen etching to elucidate the causes of such significant differences in the formation mechanism, in the physicomechanical and decorative properties (Fig. 4.11).
The structure of coatings produced from MBM-, MVM- and BM-12-type latexes was
studied. Coatings from MBM latexes were found to be characterized by a globular structure
with globules of about 30 nm in diameter. For coatings from MVM latex, the structure was
observed to be inhomogeneous, more dense by the borders of latex particles and with a
loose packing of anisodiametric structural elements inside each particle. A specific feature
of coatings formed from a dispersion of BM-12 is that they are characterized by a very fine
structure, which is not revealed using an electron microscope even when oxygen etching is
applied. The presence of this structure facilitates the coalescence of latex particles, considerably shortens the formation time of coatings, increases their strength and significantly improves their decorative properties by providing for a high gloss in the finishing of printed
matter.
These data suggest that coatings, which meet the requirements of the printing industry
small formation time, high gloss, absence of tack can be produced from polymer dispersions of the type of BM-12, which are characterized by a very fine structure of latex particles consisting of separate molecules and the occurrence of a large amount of polar groups
in their surface.
As the result of studies of the effect of the chemical composition of polyalkyl acrylates
on the structure and properties of coatings, the chemical composition of a latex was chosen,
which forms coatings with an optimal set of decorative and physicomechanical properties
satisfying the requirements of the printing products.
The effect of various physicochemical factors (pH of the medium, nature and concentration of polar groups) enabling the regulation of the decorative and protective properties

CHAPTER 4

163

b 10, MPa

Figure 4.11

Structure of latex coatings from MBM (a), BM-12 (b) and MVM (c).

5
1

50

100
, h

Figure 4.12 Kinetics of increment and relaxation of internal stresses for coatings from latexes with
different pH at 20C: 1, pH 2.5; 2, pH 5.3; 3, pH 7.7; 4, pH 7.9; 5, pH 8.2; 6, pH 8.4.

of coatings from latex with an optimal chemical composition on the formation and properties of the coatings was studied.
Dispersions with pH from 2.5 up to 8.4 were obtained by the method of hot neutralization by introducing various amounts of ammonia into the latex.
Figure 4.12 presents the data on the kinetics of increment and relaxation of internal
stresses in the formation of coatings at 20C. It is seen that the character of the kinetic curves
and the value of internal stresses depend on pH of the medium.

164

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

, 10 Pa
2
100

80

60

40
3

20

20

40

60

80
P, 10 Pa

Figure 4.13 Dependence of viscosity on shearing stress for latexes with different pH: 1, pH 3.2; 2,
pH 7.7; 3, pH 7.9; 4, pH 8.2.

The internal stresses first increase up to an ultimate value and then relax. The formation period of coatings up to extreme and equilibrium values of internal stresses increases
with pH of the medium going up. At pH from 2.5 up to 5, the formation of coatings is completed very rapidly in 1530 min, however, the internal stresses in this case are comparatively high to make 0.40.5 MPa. As pH is increased up to 7.7, the coating formation period
increases up to 4 h at considerably smaller equilibrium magnitudes of internal stresses, not
exceeding 0.3 MPa. In the subsequent increase of pH up to 8.28.4, the equilibrium values
of internal stresses are reached in 5070 h at a simultaneous increment of their magnitudes.
Figure 4.13 shows a dependence of viscosity on shearing stress for latexes with various
pH. It is seen that dispersions of acrylic copolymers at various pH values are structured systems. As pH is increased from 2.5 to 7.7, the ultimate shearing stress and viscosity of the
broken structure increase. In the subsequent increase of pH, the ultimate shearing stress decreases and the character of the rheological curves changes. At pH equal to 8.2, a sharp differential is observed between the upper and lower levels of viscosity, which is indicative of
a small number of contacts between the structural elements and a weak intermolecular interaction between them. The most structured dispersion is a latex with pH equal to 7.7. As
seen in Fig. 4.12, coatings produced from this dispersion reveal the least internal stresses.
The data on the rheological properties of dispersions were compared with the size of
latex particles determined by the method of electron microscopy.
The microstructure of latex particles obtained from very diluted dispersions of a concentration of 0.001% was studied. The diameter of latex particles was found to change nonmonotonically. As pH was increased from 3 up to 7.7, the diameter of latex particles
decreased from 0.15 down to 0.06 m and then, at a subsequent increase of pH up to 8.4,
rose up to 0.2 m.

CHAPTER 4

165

0.5 m

0.5 m

0.2 m

Figure 4.14

A peculiar feature of dispersions studied is that, starting from pH 7.7, the polydispersity of latex increases significantly, and, along with large particles of 0.06 up to 0.2 m,
globules of 1520 nm in diameter, corresponding to the size of separate coiled molecules,
were found.
These data suggest that the most structured dispersions are latexes with particle size
of 15 up to 60 nm. As the diameter of particles increases up to 200 nm, the ultimate shearing
stress decreases and the character of the rheological curves changes, which is indicative of
the fast degradation of this structure at a small increase of the shearing stress.
The occurrence of globules in dispersions commensurable with the size of coiled molecules at pH larger than 7, and a significant effect of pH on the physicomechanical properties of dispersions and coatings on their basis indicates the interaction of ammonia atoms
with carboxylic groups of polymer molecules, a decrease of the intermolecular interaction
and dispersion of latex particles at optimal pH. At a further increase of pH, ammonia acts
as an astabilizing agent promoting the coalescence of latex particles.
To elucidate the peculiar features of structure formation in the dispersion depending
on pH of the medium, the structure of coatings corresponding to the equilibrium values of
internal stresses depending on pH of the medium was studied (Fig. 4.14).
It has been found that for coatings from dispersions with pH from 2.5 up to 7 the fine
structure of latex particles is not revealed, which indicates that they are formed by uncoiled

166

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

80

b 10, MPa

1
4

60

40

20

40

80

100

200

300

400
, %

Figure 4.15 Stress strain characteristics of films from latexes with different pH: 1, pH 3; 2, pH 7.7;
3, pH 7.9; 4, pH 8.2.

densely packed molecules. At a small pH value, the capability of coalescence of latex particles becomes worse. At pH equal to 7.7, a network structure of anisodiametric structural
elements is observed. At the further increase of pH, an inhomogeneous globular structure
is formed, with the diameter of globules commensurable with the size of coiled macromolecules and their clusters. two lines
Thus, introduction of alkali contributes to the decrease of the intermolecular interaction, dispersion of latex particles and rearrangement of their constituent macromolecules.
The presence of a set of supramolecular different-size structures in dispersions with
an alkaline medium extends the formation time of coatings owing to the incompleteness of
the relaxation processes in these systems, and contributes to the nonmonotonic change of
internal stresses in the formation of coatings.
Formation of an ordered structure in dispersions with pH equal to 7.7 and coatings on
their basis promotes a sharp decrease of internal stresses and an improvement of the physicomechanical properties of latex films.
Figure 4.15 presents stress-strain characteristics of films from acrylic latexes with different pH. It is seen that films from the latex with pH equal to 7.7 have the greatest strength
at a relative elongation. The dependence of strength and relative elongation on pH of the
medium is nonmonotonic and reveals a maximum at pH 7.7. A similar nonmonotonic dependence on pH of the medium is revealed for the adhesion of coatings (Table 4.11). The
greatest adhesion is seen to be observed for coatings from a dispersion with pH 7.7.
To elucidate the cause of a sharp increase of adhesion of coatings at pH 7.7, the effect
of pH of latex on IR spectra of the coatings was studied. As the result of those studied, it
was found that a new band in the region of 1560 cm1 characteristic of free carboxyl groups
emerged on the spectrograms with the increase of pH up to 7. It is seen in Fig. 4.16, which
presents the data on the effect of pH on the concentration of carboxyl groups, that the
amount of these groups increases significantly at pH equal to 7.78.2. It follows from the
comparison of these data with the structure of coatings that at pH 7.7 the coatings feature
ooooo

CHAPTER 4

167

Table 4.11 Effect of pH of latex on the physicomechanical and decorative properties of coatings.
pH of latex

Strength p,
MPa

3.0
5.3
7.7
7.9
8.2

6.8

8.3
6.5
6.8

Adhesion A,
Relative
MPa
elongation , %
210

310
320
305

4.0
7.8
14.0
12.0
11.0

Gloss,
%

Agglutination,
MPa

3540
3540
4045
2530
2328

0.100.12
0.150.18
0.070.09
0.150.18
0.100.13

the most ordered structure from anisodiametric structural elements. A sharp increase of
adhesion at pH 7.7 is, apparently, due to the concentration of free carboxyl groups on the
surface of these structures.
100

Transmission, %

75

50

25

0
0

8 pH

Figure 4.16 Effect of pH of latex on the concentration of carboxyl groups.

The effect of pH on the kinetics of film formation is also revealed in the formation of
coatings at a higher temperature (6070C). Figure 4.17 presents the data on the kinetics
of increment of internal stresses in the formation of latex coatings at 70C from dispersions
with different pH. It is seen that the rate of the formation of coatings under these conditions
increases considerably irrespective of the pH value of the medium. However, in coatings
from dispersions with pH from 3 up to 7.7, internal stresses were observed to have some
rise as compared with coatings formed at 20C.
The effect of the nature of the polar groups on the formation process, supramolecular
structure, physicomechanical and decorative properties of coatings from latexes based on
polyalkyl acrylate was studied.
Latexes with various (carboxyl, amide, nitrile) polar groups were produced by the
method of emulsion polymerization with an equal amount of the same emulsifier (sulfanol)
and the other conditions equal by introducing 12 wt.% monomers with various functional
groups: methacrylic acid, methacrylic acid amide, acrylic acid nitrile and a mixture of

168

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

b 10, MPa

3
2

4
1

, h

Figure 4.17 Kinetics of increment of internal stresses for latexes with various pH at 70C: 1, pH
2.5; 2, pH 3.0; 3, pH 7.7; 4, pH 7.9; 5, pH 8.2; 6, pH 8.4.

methacrylic acid and acrylic-acid nitride (Table 4.13).

Table 4.12 Characteristics of latexes of different colloidal and chemical nature.


Latex

Composition and ratio of


components, wt. %
BA
30

BM-12

BMA
70

Dry
residue, %

MAA
12

46
49.0
40
40
40
40
40

sp

pH

viscosity by
VZ-4, sec

2.9
3.6
6.1
6.1
6.1
6.1
6.1

2.55
3.0
5.0
7.7
7.9
8.2
8.4

13
15
20
16
41
210
24

Table 4.13 Characteristics of latexes of different nature of polar groups.


Chemical composition and ratio of
components, wt. %
BA

BMA

MAA

AAN

AAA

30
30
30
30

70
70
70
70

12

12

12
12

12

Dry residue,
%

pH

49.7
38.5
46.2
50.4

2.65
6.3
3.1
3.4

Particle size, Surface


m
tension, ,
103 N/m
0.131
0.808
0.925
0.102

53.5
50.9
57.0
49.1

Note: BA, butyl acrylate; BMA, butyl methacrylate; MAA, methacrylic acid; AAN, acrylic acid
nitrile; AAA, acrylic acid amide.

methacrylic acid and acrylic-acid nitride (Table 4.13).


Figures 4.18 and 4.19 present the data on the kinetics of increment and relaxation of
internal stresses in the formation of coatings from latexes of acrylic copolymers with

CHAPTER 4

169

b 10, MPa

6
2

10 , h

Figure 4.18 Kinetics of increment and relaxation of internal stresses in the formation of coatings
from latexes with various functional groups: 1, COOH; 2, CONH2; 3, COOH, CN; 4, CN.

6
2
b 10, MPa

1
4

8 , h

Figure 4.19 Kinetics of increment and relaxation of internal stresses in the formation of coatings
from latexes with various functional groups at 70C: 1, COOH; 2, CONH2; 3, COOH, CN; 4, CN.

various functional groups. It is seen that the formation at 20 and 70C is completed the most
quickly for coatings from latexes containing the carboxyl groups. The greatest internal
stresses at the initial stage of coating formation emerge in the system from a latex containing
the amide groups. However, as the result of the relaxation processes during the storage of
coatings under room conditions, the internal stresses decrease significantly. By the equilibrium values of internal stresses, the coatings can be arranged in the following sequence. The
internal stresses are the greatest in the formation of coatings from a latex with the carboxyl
groups; the smallest, in coatings from a latex with the nitrile groups. Latexes with the amide
groups and a mixture of carboxyl and nitrile groups form coatings with intermediate values
of internal stresses.
These data are well consistent with the results of studies of the stresses for coatings
from a latex based on the copolymer of butyl acrylate and methyl acrylate with various polar
groups. However, the effect of the nature of the functional groups manifests itself differently on the character of the kinetic curves depending on the chemical composition of the copolymer.
The data on the kinetics of the change of internal stresses in the formation of coatings

170

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

u, % 50
40
30
CN
20

CONH2

10
COOH
0.1
Figure 4.20

0.2

3 , h

Curves of the drying of coatings of various chemical compositions.

from latexes with various functional groups were compared with their drying kinetics. Figure 4.20 presents the drying curves for coatings of various chemical compositions. It is seen
that the drying process is completed the most quickly for coatings from latexes with the carboxyl groups; the slowest drying coatings were those from a latex with the nitrile groups.
Internal stresses reach a maximum after the removal of moisture from the latex and the
emergence of the largest number of bonds between latex particles.
To elucidate the cause of the nonmonotonic change of internal stresses in the formation
of coatings from latexes with various functional groups, the structure of the film was studied
at particular stages of the film formation process by the method of replicas without their
additional treatment and using oxygen etching to reveal the fine structure of latex particles.
From the data on the structure of coatings from latexes with the carboxyl groups at the
stage corresponding to the maximum internal stresses and their equilibrium value, it follows
that in coatings from latexes with the carboxyl groups latex particles are found on unetched
specimens at the initial stage of coating formation.
In coatings from a latex with the nitrile groups under the same formation conditions,
a more dense structure is observed by the interfaces of the latex particles.
The structure of latex particles was revealed using the method of oxygen etching.
Coatings from latex with the carboxyl groups reveal a fine structure, which is indicative of the presence of a homogeneous molecular structure of latex particles. In coatings
from a latex with the nitrile groups, an inhomogeneous globular structure is observed
(Fig. 4.21).
As the result of their coalescence, no latex particles were observed in coatings from
latexes with the carboxyl groups at the final stage of formation, corresponding to the equilibrium value of internal stresses.
For coatings from latexes with the nitrile groups, owing to the rearrangement of the
structural elements, a homogeneous globular structure (revealed by the method of oxygen
etching) is observed at the final stage of formation.
The structure of latex particles, nature of polar groups and their distribution on the
surface of particles renders a significant effect on the adhesion of coatings (Table 4.14).

171

CHAPTER 4

Mixture of CN
with COOH

0.4 m
Mixture of CONH2
with CN

Figure 4.21
Table 4.14 Effect of the nature and concentration of functional groups on the properties of films.
Characteristic
of latex

Breaking Abrasion, Strength Relative Adhesion Agglutination, Gloss, %


MPa***
number turns of p, MPa elongation, A, MPa
, %
of bends* prisms**

Functional group
Carboxyl
COOH
Amide CONH2

50

300

0.80

90

0.55

0.0850.10

4055

65

400

0.58

400

0.70

2030

Nitrile CN

75

0.52

630

0.15

Mixed (COOH,
CN)
offprint without
coating
Amount of
methacrylic acid
(MAA), %:

55

350

0.80

130

0.40

0.170.20
(rupture of
paper)
very sticky
coating
0.0120.014

1520

1015

1517
3045

172

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Table 4.14 Effect


of the nature and concentration of functional groups on the properties of films.
(continued)
Characteristic
of latex

Breaking Abrasion, Strength Relative Adhesion Agglutination, Gloss, %


MPa***
number turns of p, MPa elongation, A, MPa
, %
of bends* prisms**

80

3.0

700

1.0

6
8
10
12
15

75
62
58
50
35

230
300
280

4.5
7.5
9.0
8.2

520
400
350
110

1.6
2.0
3.0
4.5
8.0

very sticky
coating
ditto
sticky
0.120.14
0.0950.10
0.0850.10

low
ditto
ditto
1520
4555
4045

*By preliminary requirements, no less than 30.


**By preliminary requirements, no less than 20.
***By preliminary requirements, no more than 0.12.

As seen in the table, coatings with the amide and carboxyl groups are characterized by
the highest adhesion equal to 0.507 MPa. The lowest adhesion is observed for coatings
from a latex with the nitrile groups. A sharp decrease of adhesion was also observed in the
introduction of nitrile groups to the copolymer of butyl acrylate and methyl acrylate. However, unlike the system we studied, this copolymer formed coatings with the highest adhesion in the presence of carboxyl not amide groups, To elucidate the cause of the high
adhesion of coatings with amide groups, we studied IR spectra of coatings from latexes with
various functional groups.
Figure 4.23 presents spectrograms of coatings. It is seen that a sharp increase of intensity of the absorption bands in the region of 3340 cm 1 and their shift towards lower frequencies for coatings from latexes with the amide groups indicates a high concentration of
the polar groups, forming the hydrogen bonds, on the surface of latex particles as compared
with latexes containing the nitrile and carboxyl groups. However, the high concentration of
1
10, MPa

80

2
3

60

4
40

20

50

100

150

300 400 500 600 , %

Figure 4.22 Stress strain characteristics of acryl coatings with different groups: 1, COOH; 2,
COOH, CN; 3, CONH2; 4, CN.

CHAPTER 4

173

Transmission, %

100
2

0
3600

Figure 4.23
3, CONH2.

3400

3200

cm1

A spectrogram for films from latexes with various functional groups: 1, CN; 2, COOH;

amide groups on the surface of latex particles not only increases adhesion of coatings on
their basis, but also leads to an instability of the system and to the formation of an inhomogeneous defect structure, which stipulates their comparatively low strength as compared
with coatings from latexes with the carboxyl groups.
Figure 4.22 presents the stressstrain curves for films from latexes with various polar
groups. As seen, the lowest strength and high relative breaking elongation is observed for
coatings from latexes containing nitrile and amide groups. The highest strength is characteristic of films from latex with carboxyl groups. The nature of the functional groups proves
to have a significant effect on the decorative properties of coatings and their tackiness.
As seen in Table 4.14, coatings from latexes with the carboxyl groups and a mixture
of the carboxyl and nitrile groups are characterized by the highest decorative properties. The
greatest tackiness and low gloss are observed for coatings from latexes with the nitrile and
amide groups. One of the most important characteristics of a decorative coating on a printing product is the transparency and light permanence of the lacquer film. Acrylic copolymers are known to form films with a high transparency and light permanence. The latexes
studied are characterized not only by a high light permanence but also form coatings capable of protecting paper from yellowing under the action of ultraviolet radiation. The latter
is very important, as photodegradation of cellulose is a surface phenomenon. Films with the
carboxyl and amide groups remained the same after 8 h of irradiation by a PRK-4 lamp
those with the nitrile groups, yellowed.
Absorption of water by a film from a latex with the carboxyl groups was significantly
lower than that from latexes with the amide and nitrile groups, and made 2% in 24 h.
Coatings on offprints from latexes with the nitrile groups have a smell inadmissible
for printing products.
Thus, coatings with the COOH group are distinguished by the lowest internal stresses
and formation time, high adhesion and good decorative properties; so it was of interest to
study the effect of the concentration of methacrylic acid on the formation process and properties of coatings.
In studies of the effect of the concentration of methacrylic acid on the formation mechanism of coatings from industrial specimens of divinyl latexes, we found that introduction
of an additional amount of methacrylic acid into the ready latex is accompanied by a nonmonotonic change of adhesion of the coatings. Adhesion is observed to be maximal at a

174

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

b 10, MPa

5
1

10

20
, h

Figure 4.24 Kinetics of increment and relaxation of internal stresses in the formation of coatings
from latexes with various percentage contents of MAA: 1, 15%; 2, 12%; 3, 10%; 4, 86%; 5, 4%.

small concentration of methacrylic acid of about 3%.


The further increase of the concentration of methacrylic acid was found to slow down
the rate of the relaxation processes and a sharp increment of internal stresses in the system.
The cause of this phenomenon is, apparently, due to the fact that methacrylic acid introduced in the latex adsorbs mainly on the surface of latex particles. At a large concentration
of methacrylic acid, the coalescence of latex particles becomes worse and the rigidity of the
system increases. Similar regularities in the change of adhesion depending on the concentration of methacrylic acid are observed for films based on natural rubber and divinyl styrene latexes.
A specific feature of latexes studied is that different amounts of methacrylic acid (from
2 up to 15%) were introduced as a monomer in the course of emulsion polymerization performed by the semicontinuous method with the triple dosage of monomer and emulsifier.
In this section, we studied structural transformations, physicomechanical and technological properties of coatings based on latexes from alkyl acrylates containing various
amounts of carboxyl groups in the polymer chain.
Figure 4.24 presents the data on the kinetics of increment and relaxation of internal
stresses in the formation of coatings at 20C. It is seen that coatings from latexes with a
small concentration of methacrylic acid (46%) are characterized by minor internal stresses. Owing to the incompleteness of the relaxation processes, their formation proceeds comparatively slowly and completes in 34 h. A lower content of methacrylic acid yields
unstable latexes forming very sticky coatings. As the concentration of methacrylic acid is
increased, the coating formation time becomes smaller and the character of the kinetic
curves of increment and relaxation of internal stresses changes. At the introduction of
1012% methacrylic acid into the reaction system the formation of coatings is completed
practically in 3040 min of drying. At a large concentration of methacrylic acid, along with
the increase of the stability of the physicomechanical properties, the internal stresses in the
coatings are observed to increase.
As the concentration of methacrylic acid is increased up to 15%, internal stresses become commensurable with the strength of the coatings and induce their spontaneous cracking in the process of formation.
Formation of the coatings at 70C (Fig. 4.25) is accompanied by similar regularities
in the change of the kinetics of increment of internal stresses depending on the concentration of methacrylic acid in the system; herewith, the relaxation processes in the coatings
from latexes with a greater concentration of methacrylic acid (812%) proceed faster than

175

CHAPTER 4

b 10, MPa

6
1

2
4

7
, h

Figure 4.25 Effect of the concentration of MAA on the kinetics of increment and relaxation of
internal stresses at 70C: 1, 15% MAA; 2, 12%; 3, 10%; 4, 86%; 5, 4%.

under conditions of hardening at 20C.


A significant rate of the increment of internal stresses in the formation of coatings from
latexes with a large concentration of methacrylic acid is stipulated by the slowdown of the
relaxation processes, which is related to a more intensive removal of moisture from these
systems. This is indicated by the data presented in Fig. 4.26 on the drying kinetics of coatings at 20C. From the comparison of the data on the kinetics of increment of internal stresses and drying of coatings, it follows that internal stresses in latex coatings sharply increase
in the second period of drying and reach a maximum after removal of moisture.
Table 4.15 Characteristics of latexes with various amounts of the third component MAA at a
constant ratio of two monomers BA:BMA (30:70).
Colloidal
characteristic of
copolymer

Amount of methacrylic acid, wt. %


15

Dry residue, %
49.9
pH
2.5
Specific viscosity
1.74
Size of particles, m 0.086
Surface tension, , 56
103 N/m

12

10

49.7
2.65
1.98
0.097
55

49.3
2.55
1.9
0.082
57

49.2
2.8
1.82
0.09
57.5

49.4
3.0
1.73
0.087
58.5

49.9
2.65
1.68
0.063
59.7

49.3
48.9
2.5
2.7
1.48
1.36
unstable
ditto
ditto

Note: (1) Dispersions with MAA of 0 to 2% are unstable and coagulate already on day 5. Films from
these latexes are very sticky. (2) In all specimens, the same amount of emulsifier sulfanol was used
during the synthesis.

Under coating formation conditions at 70C, the drying process (Fig. 4.26) is complete
in 20 min; herewith, the concentration of methacrylic acid in the system has no significant
effect on the character of the kinetic curves and the rate of drying.
As the concentration of carboxyl groups in the polymer chain increases, adhesion and
strength are observed to increase monotonically (Table 4.14). The concentration of methacrylic acid in the latex changes the stressstrain properties of the coatings. Figure 4.27

176

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

urel, % 100
80

60
at 70C

40

20
0
2
urel, % 100

at 20C

10

25 , min

60

2
3

20
10

20

30

40

60 , min

Figure 4.26 Kinetics of drying of coatings from latexes with various percentage contents of MAA:
1, 4%; 2, 8%; 3, 12%; 4, 15%.

100
1

p 10, MPa

80
2
60
40

3
4

20

50

100

200

400

600

800 , %

Figure 4.27 Effect of the concentration of MAA on the stressstrain properties of films: 1, 12%
MAA; 2, 10%; 3, 8%; 4, 6%; 5, 4%.

presents the data on the effect of the concentration of methacrylic acid on the character of
the stressstrain curves of the films.
It is seen that at a small concentration of methacrylic acid the films are distinguished
by a high relative elongation and low elasticity modulus. The change of the character of the
strainstress curves is observed for films from latexes with 12% methacrylic acid, which
are characterized by a high elasticity modulus and strength at a comparatively large relative

CHAPTER 4

177

breaking elongation. Films from latexes with 15% methacrylic acid spontaneously crack in
the formation process at stresses not exceeding 1 MPa. To elucidate the cause of this phenomenon, we studied the structure of coatings from latexes synthesized with different
amounts of methacrylic acid.
The structure of latex coatings from alkyl acrylates with various concentrations of
methacrylic acid was studied by the method of electron microscopy. It is seen that coatings
from latexes with 4% methacrylic acid reveal no supramolecular structure. At a methacrylic
acid concentration of 6%, separate globules of 25-40 nm in diameter and their aggregates
are observed. At the further increase of the concentration of methacrylic acid in the system,
the number of globules per surface unit increases. At a methacrylic-acid concentration of
15% striped structures are found, by the boundaries of which, owing to the concentration
of internal stresses, a spontaneous cracking of the coatings is observed.
It follows from these data that during the formation of coatings from latexes synthesized in the presence of a minor amount of methacrylic acid, no supramolecular structures
are formed in latex particles and coatings as the result of a strong branching of molecules
of other constituent monomers. As the concentration of methacrylic acid in the system is
increased, the intermolecular interaction goes up and, along with the fine molecular structure not revealed by electron microscopy, separate globules of 25 up to 50 nm in diameter
are observed, probably formed as the consequence of the aggregation of macromolecules.
In studies of the effect of the concentration of methacrylic acid on the coatings decorative properties determining the possibility of their use for finishing printing products, the
best gloss and absence of tack were found to occur in coatings with a high concentration of
methacrylic acid (1215%) (Table 4.14).
The entire set of data obtained indicates that coatings from latexes with 12% methacrylic acid are characterized by the best physicomechanical and decorative properties.

4.7

Specifics of forming coatings on paper and offprints

The physicomechanical and decorative properties of coatings used for finishing printed
products have been shown to depend on the structure of latex particles and coatings. High
gloss, strength, adhesion, the absence of tack, the small formation period of latex coatings
and minor internal stresses are characteristic of coatings from latexes with the homogeneous molecular structure of latex particles and a large concentration of the carboxyl groups
on their surface, which contributes to the fast coalescence of latex particles in the formation
of coatings.
When working out the formulation of compositions for coatings with optimal physicomechanical and decorative properties, suitable for finishing packaging products, developers studied the effect of the chemical composition of copolymers based on alkyl acrylates,
the colloidalchemical nature of latex, the nature and concentration of polar groups on the
structure and properties of coatings.
However, all those studies were performed in the formation of coatings on a glass support. The glass support was chosen as a model containing a considerable amount of hydroxyl groups on the surface and differing from the supports used in the printing and packaging
industry (paper, offprints) by the absence of a fibrous porous structure. This model made it
possible to exclude the effect of a specific structure of the support and its inhomogeneity
on the formation of latex coatings.
This section investigated the effect of the nature of the supports surface and the
character of its structure on the formation of latex coatings by comparing the kinetics of

178

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

increment and relaxation of internal stresses with the drying rate, depth of impregnation,
rate of absorption and the contact angle of wetting, and the decorative properties of
coatings.
The physicochemical ways for decreasing the internal stresses in the formation of latex
coatings on paper and offprints were developed by studying the effect of structuring additives and the drying method on the formation of latex coatings.
The object of the study was the latex based on polyalkyl acrylate BM-12.
As supports, we used offset papers of various densities and types (see Table) and offprints. Halftone prints were obtained under production conditions by the offset method by
applying four inks (series 2513) on paper (of the Goznak Paper Plant). The most saturated
sections of the prints were used for the study.
It is seen in Table 4.16 that the most porous papers with low sizing and large unevenness of the surface are those of the Kamenogorsk Paper Plant and the Goznak Paper Plant.
A more dense paper with the closed-up structure of pores, small porosity and high smoothness is map paper.
Table 4.16 Characteristics of papers studied.
Parameter

Bulk weight in g/cm3, no


less than
Mass of 1 cm2 in g
Breaking length (on
average in two
directions) in meters, no
less than
Fracture (number of
breaking bends) in
transversal direction, no
less than
Sizing in mm, no less
than
Ash content in %, no less
than
Smoothness on average
on the face side and grid
side in sec, no less than
Strain after soaking in %,
no more (in transversal
direction)
Moisture in % (VEB-36)
Porosity in sec

State standard Offset paper


Offset paper
GOST for Cartographic
(GOST) for No 1 (Goznak No 1 grade G cartographic
paper,
offset paper Paper Plant) (Kamenogorsky
paper
grade C
Offset Paper
Plant)
0.75

0.8

0.78

0.87

100,120
2400

120
2905

120
2500

120

120
2300

44

30

62

1.25

1.25

1.25

on average in
two directions
no less than
50
1.75

1.75

10

12

16

no less than 4

4.8

30

3762

3853

no less than
35

90110

+2.5

+1.6

+1.8

+2.2

+1.5

5.57.0

5.8
27.3

5.7
21

6.51

4.7
17

Note: In all papers, the fibre is directed longitudinally. Acclimatized conditions: equilibrium air
moisture 5560%, temperature 21C.

CHAPTER 4

b 10, MPa

24

179

20

16

12
4

8
4
2

10

12

14 , h

Figure 4.28 Formation of latex coatings on various papers and offprints at 20C: 1, Kamenogorsk
Paper-Plant paper; 2, Goznak paper; 3, map paper; 4, offprint.

Films from blue and black inks (included in the series 2513) applied to the surface of
glass prisms as a sublayer of 5-7 m thick were also used as supports to elucidate the effect
on the values of internal stresses and adhesion of the lacquer film to the surface of offprints.
Internal stresses in the formation of coatings on fibrous supports (paper, offprints)
were studied by the polarizationoptical method using the earlier developed technique for
preparing specimens, which consists in pasting paper onto the surface of glass prisms followed by the application of a film former onto it.
Adhesion was assessed by the values of ultimate critical stresses causing the spontaneous delamination of the film from the support. The effect of the nature of nonporous supports of the type of glass, black and blue inks on the kinetics of increment and relaxation of
internal stresses in the formation of coatings. It is seen that coatings are formed the most
rapidly on a blue ink sublayer, with the stable properties settled. Formation of coatings on
a blue and black ink sublayer is accompanied with a decrease of the internal stresses in the
system. However, the adhesion of coatings decreases simultaneously from 5 MPa on glass
down to 1.82.2 MPa on an ink sublayer, respectively, black and blue.
Worse adhesion of coatings to the ink sublayer is due to the fact that offset inks include
polymerizing composition drying oils based on wood rosinmaleic or phenol-aldehyde
resins, which contain in a hardened state a much smaller amount of active polar groups capable of specific interaction with the latex coating.
Figures 4.284.29 present the data on the kinetics of increment and relaxation of internal stresses in the formation of latex coatings on the surface of various kinds of papers
and offprints at 70 and 20C. It is seen that internal stresses in the formation of coatings
both at 20C and 70C on offprints and paper change nonmonotonically, the way they do
on glass. Figure 4.30 presents the drying curves of latex coatings on various papers and on
an offprint. It is seen that drying to a constant weight is completed the most quickly in an
offprint and in map paper. It is seen from the comparison of Figs. 4.25 and 4.27 that considerable internal stresses emerge at the initial coating-formation stage associated with the
elimination of moisture and the emergence of local links between latex particles. A sharp
increase of internal stresses in the formation of coatings on fibrous supports is, apparently,
due to a partial impregnation of the fibrous base and the reinforcement of the boundary layers of the coatings. However, during the storage of coatings under room conditions, owing
to the relaxation processes, the internal stresses are sharply decreased and do not exceed
0.40.5 MPa. From the comparison of Figs. 4.24 and 4.26, it follows that the relaxation processes in coatings formed on glass are completed much faster than in coatings on paper and
on an offprint.

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

32

b 10, MPa

1
24
4
16

9 , h

Figure 4.29 Formation of latex coatings on various papers and offprints at 70C: 1, Kamenogorsk
Paper-Plant paper; 2, Goznak paper; 3, map paper; 4, offprint.

u, % 100
80
60

40

20
5

10

15

20

25

30

45 60 , min

Figure 4.30 Kinetics of drying of latex coatings on various papers and offprints: 1, map paper; 2,
Goznak paper; 3, Kamenogorsk Paper-Plant paper; 4, offprint.

The cause of this phenomenon is, probably, due to a partial reinforcement of the coating by the fibrous support and to the effect of its structure on the rate of the relaxation processes. When specimens are dried under room conditions, the relaxation processes are
completed the fastest in coatings applied on to offprints.
Thus, it follows from these data that the character of the kinetic curves of the change
of internal stresses during the formation of latex coatings does not significantly depend on
the nature of the support. The nature of the surface of the support, its structure and porosity
render a considerable effect on the increment and relaxation rates, the values of internal
stresses, the formation period, the decorative properties of coatings.
The structure of various types of papers and its effect on the impregnation of paper and
offprint with latex was studied using optical and electron microscopies with the view to elucidate the specific features of latex coating formation on fibrous supports.

5
5.1

Technology
of the Development
of Canning Containers

Purpose of canning containers

Despite the development of new methods, equipment and technologies for processing food
products, canning still remains one of the methods of preserving perishable products during
the mass slaughter of livestock and delivery of milk. A broad use of canning makes possible
a gradual supply of meat and dairy products over the year and their delivery to regions distant from processing plants.
Metal containers from aluminium, chrome-plated steel or tinplate are the traditional
type of packaging for canned products in meat and dairy industry, in production of canned
fruits, juices, drinks, stewed fruits. Application of metal containers reduces labour intensity
and sterilization time, increases labour efficiency, decreases the requirement in storage
facilities.
The progress of canning industry is closely related to the development and manufacture of advanced, mainly metal, canning containers. Though they give way to polymer containers in the assortment and production rates of new types, metal containers are
nevertheless successfully used and their output is predicted to double by the turn of the
century.
In Russia, annual output of tinplate cans is 34.6 bln; of them, 26.3 bln for packaging
various food products; for alcohol-free beverages, 4.4 bln; and for non-food purposes, 3.9
bln.
In the UK, one of the leading European countries manufacturing metal food containers, production of canning containers was 3.6 bln cans for foodstuffs; 2.2 bln cans, for animal food; and 7.38 bln cans, for drinks.
According to the data by the American Iron and Steel Institute, eight leading US companies members of this institute manufacture annually 3715 thousand tons of
light-gauge tinplate, used mainly in fabrication of metal cans; including tinplate, 2611 thousand; tin-free plate, 889 thousand, and black plate, 215 thousand. On the whole, the world
demand is over 50 bln cans. The development of a new metal can takes three years on
average. This time is required to solve numerous issues: fabrication of a container and a set
of equipment; filling of the container; processing of the packaged product; reliability; air
tightness.

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

In Russia and Kazakhstan, electrolytical tinplate is manufactured on five lines; in particular, in Magnitogorsk Integrated Works of Metal Containers and Ispat-Karmet Steel
Works.
Owing to the change in the level of requirements to tinplate by processing plants,
which is due to the implementation of advanced can-producing lines and the development
of new canning container-producing technologies, these enterprises can not meet the demand on some items of assortment and quality. First and foremost, this is high-plasticity
tinplate for production of beverage cans by the deep-drawing method. There is also a deficit
of wide-format (more than 850 mm), thin-gauge and fine (0.20 and less) tinplate. Manufacturing of these types of tinplate in Russia is impossible due to the absence of respective
equipment.
The ecological and technological problems of tinplate production have been solved in
the recent decade. The quality of tinplate has been significantly improved due to the increase of the uniformity of distribution of the tin coating over the width of the band by
2535% or 0.30.4 g/m2 depending on the mean thickness of the coating; elimination of
some characteristic defects of the coatings, affecting the consumer properties of tinplate,
such as non-reflown edge and matte appearance; increase of the corrosion resistance
of tinplate by 3040% depending on the mean thickness of the coating.
An important problem is also a limited assortment. The system of assessing the quality
of tinplate does not include the set of issues related to corrosion resistance and other performance characteristics of material. Of all parameters affecting the corrosion and operational behaviour of material (lacquering, soldering, integrity), in practice only the
roughness is rated and checked. Totally excluded from the rating system are such parameters as corrosion resistance, composition of the chromate film, thickness variation of the
coating. These parameters are especially important for tinplate.
Traditional types of containers used for production of canned products are glass jars
with lids from tinplate or chrome-plated steel or aluminium. Production of canned products
in metal canning containers ensures the rise of the productivity of the process equipment,
the decrease of labour intensity and sterilization time, the reduction of the demand for
storage facilities.
In the recent years, aluminium, chrome-plated steel, aluminized steel are widely used
along with tinplate, which is in short supply. New materials are characterized by a lower
corrosion resistance as compared with hot-dip tinning and electrolytic tinning tinplate. In
this connection, other oligomers and polymers are used for protection of canning containers
along with traditional film formers, such as oil systems and epoxyphenol lacquers. The requirement in new lacquer-and-paint materials is also due to the production of metal canning
containers of changed design (deep-drawn cans, composite cans with soldered seam, twopiece stamped and composite cans, readily opened lids, special lids for glass containers,
tubes).
All this specifies the high requirements to lacquer-and-paint coatings intended for protection of containers, with respect to adhesion, physicomechanical properties and resistance
to the action by canned products in their long-time storage. At present, coatings of canning
containers are produced using phenolic-oil, epoxy, acrylic, polyester etc. bonding adhesives as film formers.
A broad assortment of lacquer-and-paint materials for protection of metal canning containers is due to the fact that at present there is no universal paintwork material suitable for
any metal support and canned product. The diversity of materials used to produce canning
containers and the difference of the properties of products packaged into them make it

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183

necessary to develop diverse lacquer coatings ensuring the protection of containers and
products under various technological conditions of production, canning and storage.

5.2

Field of application and efficiency of use

When producing containers for packaging meat, dairy, fish, juices and fruit-and-vegetable
canned products, tinplate due to the deficit and appreciation of tin is increasingly more
often replaced with aluminium and its alloys, although they are more expensive than tinplate (1015% or, by some other information, 25%).
Aluminium possesses a number of properties, which make it indispensable container
material: light weight (density of aluminium is almost 3 times larger than that of tinplate),
good formability, plasticity, high protective properties, heat resistance; resistance to water,
gases, smells, fats, action of bacteria and pests; high reflectivity; good protection of the
product from the action of heat and cold; possibility of combining it with other materials.
Increased use of aluminium materials is also stipulated by the development of aceptic
canning, increased production of frozen foods, increased demand of extended storage time.
Prospects of the further application of aluminium are determined not only by its merits,
but also by the reduction of costs for reprocessing of discarded containers. On average, 1
ton of aluminium is required to fabricate 32 thousand cans; 1 ton of tinplate, only 15 thousand. Expenses for the fabrication of an aluminium container are on average 1% of the cost
of canned product it contains.
According to the data by US companies, production of 1 kg aluminium from bauxites
requires 18.6 kW h of electric energy and 57.1 kJ of thermal energy. These data also include
total energy costs for extraction of ore, its processing and melting, as well as transportation,
heating, illumination, collection and utilization of wastes.
In production of an aluminium sheet, a considerable part of material charged into the
melting furnace is scrap of all sorts, including used aluminium containers. This type of secondary raw materials should be subjected to pretreatment, which includes its cleaning and
removal of the lacquer coating. With the required energy expenses in mind, as well as additional consumption of energy for transportation, illumination and heating, the total consumption of energy for melting of 1 kg of aluminium from scrap is 0.11 kW h of electric
energy and 8.0 kJ of thermal energy. Therefore, production of aluminium from secondary
raw materials requires only 0.6% of electric energy and 13.8% of thermal energy necessary
for production of this material from ore.
The ratio between the total reduced energy intensity of the treatment of primary and
secondary aluminium raw materials is 28.5:1. Calculations performed by US companies
have shown that collection and reprocessing of 60% of used aluminium containers reduces
the total energy intensity of container production almost two times. Two major US companies Reynolds Metals and Alcoa annually collect and reprocess over 200 thousand tons of
used aluminium containers, which enables the output of about 9.6 bln cans. These companies utilize about 75% of containers produced. On the whole in the USA, about 60% of aluminium cans and packs are utilized annually, which makes possible the re-use of 650
thousand tons of aluminium.
In France, 27% of aluminium is produced from secondary raw materials. In Sweden,
about 80% of manufactured aluminium packs are reprocessed. However, there are organizational problems of collecting, sorting out and transporting the used aluminium packs. On
the whole, the return of this metal to the production cycle can reach 50150 bln tons per
year.

184

5.3

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Requirements to the properties of coatings for canning containers

The purpose of a lacquer-and-paint coating is to protect the surface of canning containers


from the action of food products. The larger is the continuity of a lacquer-and-paint coating,
the lower its permeability is, and, therefore, the more reliable its protection properties are.
The major requirement to lacquer-and-paint coatings is their continuity, as well as chemical
endurance, mechanical strength and high adhesion.
The performance properties of coatings for protection of metal canning containers depend on the composition of their ingredients, the physicochemical and technological properties of lacquers and enamels.
Of great importance is the ability of film-forming solutions to spread well and be well
distributable on metal upon application. Viscosity of the lacquer-and-paint materials and
the dry residue content are also of great significance.
Protection of the inner and outer surface of canning containers is provided for by the
use of mainly lacquer-and-paint materials, which harden at high temperatures from 180 up
to 360C.
The physicomechanical properties of coatings are determined by the structure of polymer macromolecules. Linear and network polymers under the action of an external force
change their properties differently. Network polymers extend in tension insignificantly and
then break down. Linear polymers are deformed in tension, then a thickening appears on
specimens at the further increase of stresses, and polymer extends four and more times with
the orientation along the extension axis of macromolecules and their aggregates.
Linear polymers are characterized by three major types of strain: elastic, rubberlike
and plastic. Elastic strain is caused by large stresses and is due to the change of interatomic
distances in polymer crystals or molecules. They are totally reversible and do not exceed
1%. Rubberlike strains can reach 1000% and are totally reversible; however, the initial
shape is recovered not immediately but in time.
Plastic strain of polymers is irreversible. It is associated with the regrouping of macromolecules or their aggregates relative to one another. The process of changing the state
of stress in transition from an inequilibrium arrangement of its structural elements to the
equilibrium state is stipulated by the relaxation of stresses. Relaxation phenomena are especially dangerous for those technological processes, where the strongly deformed coating
is under the action of high temperatures.
The disturbance of a polymer coating, due to the formation of cracks, a partial delamination and other defects can be observed in thermal sterilization in the container fabricated
by deep drawing from lacquered tinplate or aluminium, as well as in drying of the sealing
paste on lids pressed from lacquered tinplate.
Internal stresses can occur in coatings not only as the result of their deformation upon
film formation, in particular in drying of coatings, but also as the consequence of inhomogeneity and imperfection of the structure. Inadmissible shrinkage of a polymer coating in
the process of drying is determined by the decrease of its volume at an invariable surface
area of the material. The cause of shrinkage is the removal of solvent and the polycondensation reaction in coatings with evolution of side products of the reaction. An increase of
the molecular mass of the film former leads to a larger shrinkage of the film; solvents with
a smaller vapour pressure, as less volatile ones, contribute to the decrease of shrinkage of
the coatings.
To reduce the shrinkage of coatings in fabrication of metal container materials, their
thickness should be decreased down to 36 m. If thicker coatings up to 1218 m

CHAPTER 5

185

are to be applied, for instance, for protection of black plate, they are applied, as a rule, in
two or three layers.
A large role in defining the protective properties of coatings is played by the adhesion
properties. Adhesion is determined by the force of interaction of two contacting surfaces of
materials different by their nature. The extent of adhesion of a film to a solid surface is assessed by the force spent for its delamination from the support. At strong deformations of
material in fabrication of containers and partial destruction of the coating, three types of
adhesion disturbances are observed:
adhesion forces are stronger than cohesion forces, peeling-off occurs by the material
of the coating; this is the cohesion detachment of the film;
adhesion forces are smaller than cohesion forces, peeling-off occurs by the area of
the contact of the film with the support; this is the adhesion detachment of the film;
adhesion forces are approximately equal to cohesion forces, the mixed peeling-off
occurs; this is the adhesioncohesion detachment of the film.
When applying a lacquer-and-paint coating to the metal surface at the first stage of the
process in the liquidsolid system, adhesion forces exceed cohesion forces significantly.
However, as the film-formation process proceeds further, cohesion forces increase and in
most cases start to exceed those of adhesion.
Formation of a polymer film includes a complex of processes chemical, physicochemical, electrostatic, as well as mechanical interaction of the polymer coating with metal.
The value of adhesion is greatly affected by the state of the surface and its microgeometry,
as well as the nature of the film former. The more the amount of active polar groups in the
composition, such as hydroxyl, carboxyl, epoxy etc. groups, the stronger the interaction of
the polymer coating with metal is.
Lacquers based on comparatively low-molecular-mass substances (phenol formaldehyde and epoxy oligomers) form films with good adhesion owing to the high mobility of
molecules and their orientation at the interface.
The nature of forces responsible for adhesion is defined differently in works by different authors. According to the electrostatic theory, adhesion of polymer coatings to metal is
explained by the electrostatic attraction of the charges of the double electrical layer by analogy with microcapacitors, whose interfaces are films of polymer and metal. Considering
that adhesion of various kinds of lacquer-and-paint materials is different and depends on
the nature of metal, the method used in practice consists in using special systems of coatings, such as primercoating systems. In this case, the coating consisting of two layers of
polymer provides for adhesion to any of these materials. Of crucial significance in this case
is the diffusion phenomenon, which provides for a strong cohesion of two polymer film
formers. When considering the phenomena at the metalpolymer interface, the crucial factor in its determination is the formation of special bonds providing for the chemical interaction.
Permeability of polymer coatings is one of the main characteristics determining its
protective properties. It depends on the following major factors:
molecular permeability, which is determined by the nature of polymer, molecular
structure, packing density of molecules;
nature of a lacquer-and-paint material and its preparation;
process procedures in application and formation of coatings.
Chemical endurance of polymer coatings depends on the nature of a film former, as
well as on the conditions of chemical reactions leading to the formation of a crosslinked
molecular structure.

186

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Oleo-resinous lacquers are characterized by an insufficient chemical resistance, which


is affected by the drying oils in their compositions, owing to the large content of ester
groups subjected to oxidation and determining the swelling of coatings in aggressive media.
Resistance of coatings to ageing in the process of operation is determined by the extent
of deterioration of the mechanical properties, such as elasticity and shock resistance. This
process is determined by the following factors: destruction of the film former, occurrence
of chemical reactions, loss of the plasticizer or residual solvent by the film, rate of the relaxation processes.
The film former can be destroyed under the action of light, oxygen, high temperatures
or aggressive media. As the result of the destruction, the molecular mass decreases, the
strength and elasticity of the coating go down. Ageing of the films due to the erosion or
blooming of plasticizers and residues of solvents is of no great significance for can varnishes, as they are not used in formulations of varnishes, and the coatings are dried at high
temperatures.
The effect of factors that accelerate ageing is attenuated by using antioxidants as additives. Introduction of pigments, such as aluminium powder, titanium and zinc dioxide
slows down the ageing process, as the formation of various aggressive substances in liquid
and gaseous state is made difficult.

5.4

Coatings for protection of canning containers

The corrosion resistance of aluminium is insufficient for most food media; an additional
protection is required, which is done by anodization followed by lacquering the metal. The
type and stability of can varnishes mainly determine the possibilities of using metal container materials. Owing to the protective property of a varnish, the canned product is separated from the metal of the can. If metal is not lacquered, then sweet, sour, salt- or
protein-containing food products cause its corrosion. The action of metal compounds
formed as the result causes changes of the appearance, colour and taste of ready-prepared
products, reduce the integrity of sterilized preserves. Application of a lacquer coating on
the surface of chrome-plated plate decreases the rate of penetration of iron and chromium
into the product tenfold.
The protective lacquer coating should have the following properties: a good adhesiveness to metal and a corrosion resistance; inertness with respect to a food product; a good
capability of deep drawing; a maximal resistance to strain, action of hot water and acids, as
well as to sterilization and pasteurization; a large range of applications for various food
products; processibility, stability of the properties of compositions in storage (no less than
1 year); the possibility of coating thickness variation within wide limits; formation of an
almost pore-free lacquer film with a high scratch resistance at its weight of 58 g/m2 of the
film; a small duration of hot drying, no more than 3060 sec to achieve an optimal
crosslinking of the polymer using a high-capacity equipment; a possibility of endowing the
antiadhesion properties, preventing the adhesion of the contents to the can.
These requirements are met using epoxyphenol and oleo-resinous lacquers; enamels
with zinc oxide, titanium dioxide and based on polyvinyl chloride and copolymer of vinyl
chloride; lacquer-and-paint materials from water-diluted, -soluble, -dispersion bonding adhesives, as well as systems with a high content of film former; powder inks.
Various raw materials and semi-finished products mainly synthetic oligomers and
polymers are used to produce lacquer-and-paint materials intended for protection of metal
canning containers. To modify some of them, natural products are used plant oils,

CHAPTER 5

187

products of wood rosin reprocessing. Enamels are prepared with application of mineral pigments, such as zinc oxide, titanium dioxide and aluminium powder. To dissolve
lacquer-and-paint materials, organic solvents are used.
Plant oils are produced from seeds or fruits of oil-bearing crops. The major component
of plant oils (over 95%) are glycerol esters of fatty acids (triglycerides) containing from 14
up to 18 carbon atoms.
The properties of oils depend on the composition and structure of fatty acid radicals,
which are components of the esters. In particular, the ability to dry is determined by the
number of double bonds in the triglyceride molecule, as well as by their mutual position.
By the drying ability, oils are divided into the following groups: oils with the greatest drying
ability, drying oils and semidrying oils.
Castor oil is used in production of lacquers in dehydrated form. It is distinguished by
a number of valuable properties and is close to Chinese wood oil. It is widely used abroad
in production of can varnishes, in particular, to produce protein-resistant coatings. It is also
used to produce dimerized acids, which are used in the synthesis of epoxy esters.
Maleinized oil is obtained by the interaction of oil with maleic anhydride; it is attached
to the fatty acid radical by the side of the coupled bond. As the result of maleinization, the
oxidation of oils slows down, and they dry slower in the air than the initial products.
For protective coatings, wood rosin modification products are used. By its chemical
composition, wood rosin of plant origin is a mixture of resin acids. The most stable isomers
are abietinic, dextropimaric and levopimaric acids. In lacquer-and-paint industry, mainly
wood rosin ethers are used, which are a product of etherification of resin acids of wood rosin
by pentaerythritol.
As film formers, epoxy oligomers are used, which are compounds whose molecule
contains no less than two epoxy or glycide groups, at the expense of which there occurs the
formation of a three-dimensional network structure in the hardening of coatings.
The main advantage of epoxides is high adhesion to most materials, the physicomechanical properties and chemical endurance, determined by the absence of readily
hydrolyzed functional groups in their composition.
As hardeners of the compositions, the most frequently used substances contain amino
groups, anhydrides of organic acids, phenol- and aminoformaldehyde oligomers, isocyanates. A disadvantage of the epoxy coatings is their low stability to stamping.
Epoxy ester oligomers are used to fabricate lacquer-and-paint materials, including can
varnishes. Widespread materials are epoxy esters of fatty acids of plant oils, as well as synthetic fatty acids with the radical length C10 C13 and C10 C16 in a mixture with fatty acids
of flax oil. Modified oligomers in production of can varnishes include alkyd epoxy resin of
grade E-30. It contains glycerophosphate GF-019 and epoxy resin E-40. Resin E-30 is used
as a bonding adhesive in epoxyphenol lacquers.
Lacquer EF-0188 belongs to epoxy esters. It is the product of etherification of epoxy
resin E-44 by fatty acids of flax oil.
The same group of film formers includes epoxy ester of grade EM-34. It is a ester obtained in the interaction of epoxy resin E-40 with monomer methyl esters of acids. This
composition is used to produce white enamel.
Production of can varnishes, along with melamine-formaldehyde oligomers, makes
use of the derivatives melamine-acetoguanamine and benzguanamine. A complex of high
physicochemical and technological characteristics of these oligomers, as well as the admissibility of their contact with food media specify the possibility of their use for production
of can varnishes.

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Epoxy esters based on dimerized acids of dehydrated castor oil are used in epoxyphenol can varnishes to increase their flowability. The coatings on their basis are characterized
by high adhesion, elasticity and chemical endurance.
Phenol-formaldehyde oligomers used to form coatings of canning containers are a
product of polycondensation of mono- and polybasic phenols with aldehydes, mainly with
formaldehyde.
Phenol-formaldehyde oligomers based on a mixture of phenol with o-cresol, n-tertbutyl phenol and technical-grade xynenols are produced under industrial conditions.
Carbamide-, melamine- and benzguanamine-formaldehyde oligomers for canning
containers are obtained by polycondensation of carbamide, melamine or benzguanamine
with formaldehyde in a neutral or weakly alkaline medium. These oligomers are widely
used in lacquer-and-paint industry as a constituent part of many canning materials.
Oligoesters are used to produce can varnishes. They are obtained by the polycondensation reaction of polyatomic alcohols with polycarboxylic acids or their derivatives. Can
varnishes based on oligoesters are synthesized using benzguanamine or melamine-formaldehyde resins, which contribute to the increase of chemical resistance of films. Coatings
hardened at 180200C for 10 min withstand boiling and sterilization.
Polyvinyl chloride and its copolymers have lately found wide use, especially abroad,
in production of can varnishes. Copolymers of vinyl chloride with vinyl acetate or with mixtures of vinyl acetate with maleic anhydride or acrylic acid, as well as copolymers of vinyl
chloride with partially saponified vinyl acetate, are used the most frequently. Coatings
based on these copolymers should satisfy stringent requirements to the content of residual
monomers and emulsifiers in products, absence of off-flavour and smell, which determines
their sanitary-hygienic properties.
For coating the outer surface of canning containers of food purpose, lacquers based on
polyacrylates are used. They represent copolymers based on acrylic CH2 =CHCOOH and
methacrylic CH2 =C(CH3)COOH acids and their derivatives, such as methyl methacrylate, butyl methacrylate, acrylamide with the general formula CH2 =rC(CH3)COR. Acrylic
copolymers are well soluble in esters of aromatic hydrocarbons, ketones.
Coatings on their basis are characterized by a high thermal stability, hardness, resistance to mechanical loads.
Polyvinyl acetals are also used for production of canning containers. They are produced by the interaction of polyvinyl alcohol with aldehydes. They are a valuable raw material for lacquer-and-paint industry. For this purpose, polyvinyl butyral a product of the
interaction of polyvinyl alcohol and butyl aldehyde - is produced in this country on an industrial scale. Polyvinyl butyral combines with alkyds; phenol-, carbamide- and
melamine-formaldehyde; epoxy oligomers, cellulose nitrate, natural resins, various plasticizers. In this connection, polyvinyl butyral is widely used in production of lacquers, enamels, primers and powder inks for protection of canning containers, items from steel and
aluminium.
Along with film formers, the composition for coating canning containers includes solvents, pigments, hardeners, modifiers. Most polymer coatings are applied from solutions.
By their chemical composition, solvents are divided into several classes: aliphatic and naphthenic hydrocarbons, for instance, white spirit; aromatic hydrocarbons (toluene, xyol, solvent naphtha); terpenic hydrocarbons (turpentine); alcohols (ethanol, butanol, etc.); ketones
(acetone, methyl ethyl ketone, cyclosanone); ethers and esters (ethyl acetate, butyl acetate,
cellosolve).
The most important requirements to solvents are their dissolving power, incombusti-

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bility and toxicity. Upon evaporation of the solvent, the film should have no smell.
Pigments are introduced into lacquer-and-paint materials to obtain filled coatings. In
most cases, they endow the coatings with a corrosion resistance and can be corrosion inhibitors. Pigments also contributed to fabrication of coatings resistant to processes of atmospheric ageing and possessing decorative properties.
Aluminium powder produced from aluminium-containing raw materials looks like
scales 0.20.5 m thick and 250 m wide. The content of aluminium in the raw material
should be no less than 99%. For lacquer-and-paint industry, aluminium powder is manufactured as paste. It is fabricated from aluminium powder of grades A-5E, A-5, A-6, A-7.
White spirit is used as a solvent.
Zinc white paint by its chemical composition is zinc oxide a white crystalline powder with the size of particles of 0.11 m. The content of zinc oxide in the pigment is
98.099.7%. Being a weakly basic pigment, zinc white dissolves in acids and alkali. It reacts to free fatty acids of oil-containing film formers.
Colloidal zinc oxide is used in production of protein-resistant enamels for protection
of canning containers.
Titanium dioxide is a white pigment. It is produced in two rutile and anatase modifications. The content of the base substance in titanium dioxide manufactured by the industry should be no less than 9598%.
Titanium dioxide is used in production of lacquer-and-paint materials for external and
internal protection of metal canning containers. Coatings based on these compositions are
resistant to aggressive canning media and external effects.
An important component of the compositions are hardeners. In production of canning
containers, the hardeners used are reactive compounds introduced into lacquers and enamels based on various film formers (epoxy, acrylic, polyester ones and copolymers of various
chemical compositions). Phenol-formaldehyde and aminoformaldehyde oligomers, polyesters, anhydrides of carboxylic acids, isocyanates are used as hardeners.
Catalysts are introduced into the compositions in minor amounts to accelerate the
hardening process. In some cases, they make it possible to reduce the temperature of hot
drying. In some cases, catalysts are used together with hardeners; for instance, orthophosphoric acid, mono- and dibutyl esters of phosphoric acid are used for epoxyphenol lacquers,
as well as tetrabutoxytitanium, para- and orthotoluene sulphoacid, aluminium alcoholate.
One of the components of a film former are gliding additives. They are introduced to
endow the coating with a resistance to scratching in the mechanical treatment of lacquered
tinplate in fabrication of metal container from it; for instance, additive PVO-30. It is oxidized polyethylene wax and is used as a 5% solution in xylol.
To improve the flow behaviour of lacquers and to eliminate crates on the surface of
coatings in the application of lacquers and enamels, special additives are introduced into
them, for instance, lacquer KO-815. Abroad, the formulations of lacquers include additives
on an acrylic or silicone basis to improve the flow behaviour, for instance, products of
grades BIK-304 or BIK-344 manufactured by German firms.

5.5

Compositions based on oligomer systems

A number of requirements are imposed on the lacquer-and-paint materials intended for internal coating of canning containers: they should not contain toxic components, be sufficiently stable in storage and provide for an even and smooth film on the surface of metal at
the application and drying of lacquer-and-paint materials. Coatings on the basis of these

190

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systems should possess a good adhesion to metal, elasticity, hardness and strength to be able
to withstand die stamping, seaming, sealing and other mechanical operations in production
of cans and lids.
Home industries manufacture epoxyphenol lacquers used for protection of canning
containers from tinplate, aluminium alloys and chrome-plated steel. The composition of
these lacquers includes various epoxy oligomers, differing by their molecular mass; phenol-formaldehyde oligomers based on various phenols and their mixtures. The high content
of phenol-formaldehyde oligomers contributes to high chemical endurance of the coatings.
Phenol-epoxy lacquer FP-559 is a solution of a mixture of resins xylene phenol
formaldehyde KFE, epoxy E-05K and alkyd epoxy E-30 in a mixture of organic solvents.
The lacquer is applied on tinplate sheets on roller-type lacquering machines; and on the inner surface of one-piece cans, on spray-type lacquering machines.
The predominant component of lacquer FP-559 is phenol formaldehyde, so at a high
chemical stability of coatings on its basis they are distinguished by a low elasticity. For this
reason, it can not be used in production of one-piece cans.
Epoxyphenol lacquer EP-547 is a solution of a mixture of epoxy E-05K and phenol-formaldehyde FP-1 resins in a mixture of organic solvents. It is used mainly for coating
tinplate in production of canning containers. The lacquer is applied on tinplate sheets on
roller-type lacquering machines and is hardened in convection-type furnaces at 200210C
in 1215 min.
As compared with FP-559, lacquer EP-547 forms films of better elasticity, which enables its use in production of one-piece containers. However, the chemical endurance of
coatings based on this lacquer, especially in an acidic medium, is lower than that of coatings
from lacquer FP-559, which restricts the areas of its application.
Lacquer EP-547 is widely used also for lacquering tubes for food and perfumery products. In fabrication of canning containers for strongly aggressive food media, tomato paste
and tinted stewed fruits, lacquer EP-547 is used in combination with other lacquers and
enamels, such as FP-559, EP-5147al, EP-5195p. Coatings on the basis of these compositions play the role of a sublayer. Chemical endurance of coatings based on lacquer EP-54
is increased by introduction of hardening catalysts of the type of tetrabutoxytitanium or chelate compounds of aluminium.
Epoxy phenol lacquer EP-527x is a solution of epoxy E-05K, phenol-formaldehyde
FPF-1 and alkyd epoxy E-30 resins in a mixture of organic solvents. This lacquer is used
mainly for coating chrome-plated steel.
Drying of the lacquer film is performed by high-frequency currents in inductors at a
temperature of up to 350C for 35 s. To increase the chemical endurance of the coating
and extend the applications of containers from lacquered chrome-plated steel, two-layer
coating is recommended to be done.
Epoxy phenol lacquer EP-5118 is a solution of epoxy E-04kr and phenol-formaldehyde FKoF-4 resins in a mixture of organic solvents. The lacquer is characterized by a high
content of epoxy resin. The lacquer is used for inner and outer coating of the band from
aluminium alloys. On the surface of metal, the lacquer is applied by the roller method. The
regime of its drying is 30 s at 340C. The advance rate of the band during the application
of the lacquer is 60 m/s.
Aluminium enamel EP-5147al is a solution of a mixture of epoxy E-05K, phenol-formaldehyde FPF-1, alkyd epoxy E-30 resins; aluminium paste, polyvinyl butyral and
special additives.
Coatings based on this enamel are resistant to the action of protein-containing

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191

products. It is used for coating cans for meat, fish and vegetable canned products.
To improve the physicomechanical parameters of coatings, primarily, scratch resistance, the enamel is applied over a thin layer of lacquer EP-547. This coating is used for
protection of containers for most types of fish preserves.
Seam lacquer EP-5186 is a mixture of solutions of epoxy E-05K and E-30 and phenol-formaldehyde FPF-1 and FKoF-4 resins in organic solvents. This seam lacquer is used
for protection of the soldered side seam of composite electrolytic-tinplate cans. The lacquer
is applied after soldering the seam, by means of pneumatic spraying and a working viscosity
of 1315 s by VZ-4. This viscosity provides for a lacquer film of 34 g/m2 thick; the width
of the lacquer coating lane is 1520 mm. The lacquer dries up due to the residual heat after
soldering and additional drying together with lacquer of grade EP-5194 at 175C for 15
min.
Lacquer EP-5194 is a mixture of solutions of epoxy resins EO-4kr and E-30 with phenol-formaldehyde resin FPF-1 in organic solvents. This lacquer is used for additional protection from corrosion of the entire inner surface of two-piece canning containers, as well
as for covering the lead-containing solder. This lacquer is applied by pneumatic spraying
and is dried for 15 min at 175C.

5.6

Oleo-resinous lacquers

An advantage of coatings based on these lacquers are their high physicomechanical properties, water and salt resistance. A disadvantage of the coatings is the low stability as compared with epoxyphenol materials. These lacquers are used for protection of containers for
certain type of preserves, for instance, crabs.
Lacquer FL-560 is a solution of the product of condensation of phenol-formaldehyde
resin 101 with Chinese wood oil. A mixture of turpentine with white spirit is used as a solvent. The drying is accelerated by using a manganese resinate siccative.
The lacquer is used for coating tinplate cans for crab preserves. This lacquer is characterized by the following technical parameters: a homogeneous and clear solution, viscosity by VZ-4 at 20C, 95120 s; drying time at 185190C, no more than 30 min.
Lacquer FL-561 is a solution of the product of condensation of phenol-formaldehyde
resin with a mixture of oxidized flax oil and dehydrated castor oil in turpentine. A cobalt-manganese siccative is used to accelerate the drying of the lacquer.
This lacquer is used for coating tinplate, which is applied in fabrication of canning containers for preserves with a neutral medium. The drying time of the lacquer at 185190C
is 30 min.
Lacquer FL-5157 is used in production of protein-resistant enamel for protection of
canning containers from tinplate, intended for crab and neural-medium fish preserves. The
cobalt-manganese siccative is used to accelerate the drying of the lacquer. The viscosity of
this lacquer is 7080 s, the content of volatiles is about 55%, the duration of hardening at
180C is 2630 min.
Lacquer KF-281 is used as a protective coating of an enamel composition based on
lacquer FL-5157. It is the product of condensation of fatty acids of flax oil and Chinese
wood oil with pentaerythritol ester of wood rosin. The lacquer contains the cobalt-manganese siccative. The viscosity of the ready-to-use lacquer is 1830 s, the content of volatiles
is about 64%, the drying time at 180C is 2630 min.
Enamels with zinc oxide are manufactured as protein-resistant ones. They are distinguished by an increased resistance to canned protein media, as zinc oxide is dispersed into

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lacquers and binds sulfurous compounds evolving in sterilization and storage of protein-containing preserves.
To increase the decorative, hygienic and anticorrosion properties of coatings, use is
made of lacquer-and-paint materials with the anticorrosion neutral pigment titanium dioxide. The major parameters of lacquer-and-paint materials for internal protection of canning
containers are given in Table 5.6.1.
Table 5.6.1 Comparative characteristics of canning containers.
Lacquer

Viscosity Content of Hardening Duration of


(by VZ-4), nonvolatiles, temperature, hardening,
sec
%
C
min

FL-559

80115

4550

180185

1215

EP-547

90120

3842

205210

1215

EP-527h 100150

3845

375385

40 (45)

EP-5118 110180

3640

335345

3540

FP-560
95120
FP-561 140170
EP-5186 5080
EP-5147 100150

5054
4952
4248
3845

185190
185190
175180
210215

30
30
15
15

EP-5194

4550

190200

15

90130

Field of application

Glass-container lids, tinplate


containers
Composite containers from tinplate
(elongation ratio, up to 0.4)
Lids and cans from chrome-plated
steel
Aluminium lids and cans
(elongation ratio, up to 0.6)
Composite tinplate containers
Ditto
For lacquered seam
Composite and pressed/punched
containers
Cans and tubes

Note: Thickness of film in these coatings changes from 4 up to 8 m depending on the chemical
composition of a lacquer.

5.7

Polyvinyl chloride-based lacquers

These lacquers also include other bonding adhesives, in particular, alkyd, phenol and epoxy
resins. The major advantages of coatings based on these copolymers is their high elasticity,
good adhesion, especially to aluminium and alloys, as well as an almost complete absence
of the transfer of off-flavours from the coating to the canned products.
Hardening of films based on vinyl copolymers occurs as the result of evaporation of
the solvents and during the lacquering of tinplate in convection-type conveyor furnaces.
The duration of drying is 10-12 min at 120185C. In application of vinyl lacquers on the
aluminium band the drying is usually accelerated 3040 s at 250275C. When using
lacquers based on vinyl copolymers, it is necessary to take into consideration the possibility
of destruction of the bonding adhesive at a drying temperature above 185C. Primarily they
are used for lacquering cans for beverages.
Coatings practically do not transfer foreign smells and off-flavour to the contents of
the can. Another important application are lids for glass containers.
A disadvantage of lacquer-and-paint materials on vinyl basis is the inconstancy of their
properties in storage of no more than 46 months. The difficulty of preparing stable dispersions is the complexity of purification and scarcity of components, a higher consumption
of lacquers on vinyl basis as compared with epoxyphenol compositions, as well as in most

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cases a low chemical stability due to the difficulty of achieving a high and stable adhesion
of vinyl lacquers to the protected surface.

5.8

Oligoesters and water-base, water-soluble and water-dispersion


binders

A promising trend in the development of lacquer-and-paint materials for protection of the


outer and inner surface of canning containers is the creation of lacquer and pigment systems
based on saturated oligoesters. Such materials combined advantages characteristic of epoxyphenol and generic systems. Coatings based on oligoesters, along with high adhesion,
thermal and corrosion resistance, possess a high elasticity, hardness and resistance to mechanical loads.
Oligoesters are used as film formers for can varnishes independently or in combination
with thermosetting oligomers, for instance, epoxy, phenol, melamine- and benzguanoformaldehyde and thermoplastic polymers (vinylic, acrylic).
Water-based lacquer-and-paint materials occupy one of the leading places in the assortment of ecologically adequate kinds of lacquer-and-paint products in most developed
countries. A significant part of the total volume of lacquer-and-paint materials on water basis are supplied to the US canning industry and are used for anticorrosion protection of containers intended for packaging beer and alcohol-free beverages. Western companies
manufacture a wide assortment of water-based lacquer-and-paint materials based on epoxy,
vinyl, acrylic polyester and other resins used in formulations of lacquers for protection of
canning containers.
In the recent years, great attention is given to the development of water-dispersion systems for protection of canning containers based on carboxyl-containing epoxyacrylic film
formers, obtained by way of physical or chemical modification of epoxy oligomers by acrylates. These lacquers were first introduced in the US canning industry, and at present more
than half of all beer cans are manufactured using water epoxyacrylic systems. Phenol- or
melamine-formaldehyde resins are used as hardeners; herewith, tertiary amines serve as a
neutralizing agent. Coatings are hardened in several seconds at a temperature of about
200C. Their advantages are high elasticity and correspondence to the sanitary-hygienic requirements to food-purpose coatings.
Changes in the recent years in the assortment of lacquer-and-paint production under
the influence of causes of economic and ecological character affected the canning industry
to a significant extent. Ecologically adequate lacquer-and-paint materials powder materials, with high content of nonvolatile components, aqueous, of radiation hardening started to be widely used for protection of the inner and outer surface of metal canning
containers. Thus, demand for such materials in the USA is over 20%; herewith, water-diluted materials are used to cover over half of beer and drink cans. In the nearest years, this
index would reach 100%.
A significant growth of demand for such compositions is due to the decreased content
of solvent, whose amount does not exceed 1520% as compared with traditional lacquers.
Their advantages are also low toxicity, fire safety, simplicity of application methods. However, for protection of canning containers only those systems are suitable, which satisfy specific requirements to materials in contact with food products. The major of them are
inertness of the coating as compared with the canned product, stability of materials in storage for no less than 12 months, processibility, high adhesion to metal supports, stability to
the action of hot water and acids, stability to sterilization and pasteurization. Coatings from

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

water-diluted materials should be of high quality, should not be inferior than traditional lacquer coatings by their performance characteristics and economical efficiency.
The most widespread water-diluted canning materials are carboxyl-containing epoxy
oligomers and epoxyacrylates. These oligomers are synthesized by various methods. The
simplest of them envisages the interaction of an epoxy oligomer with dibasic acids or their
anhydrides. Disadvantages of these methods are process problems associated with the
two-stage character of the synthesis, large duration of the process, and high cost of the product. Aqueous materials, which are distinguished by a high stability and processibility, are
obtained in the reaction of epoxy oligomers with various aromatic amino acids. These compositions are hardened in 10 min at 204C to form coatings stable to the action of acidic
and protein food products.
As a phenolic component, use is made of epoxy oligomers modified by polyfunctional
phenols. In the West, such oligomers are hardened using amino-, urea- or phenol-formaldehyde resins. Compositions are hardened in 212 min at 200215C to form coatings stable to pasteurization, sterilization; action of acids, alkali and solvents. However, the most
widely used materials for protection of canning containers are water-diluted materials based
on epoxy oligomers modified by acrylates. According to estimates by experts, these materials are used to cover over 60 bln cans.
A number of works note that aqueous materials based on mixtures of epoxy oligomers
with acrylates do not always satisfy manufacturers of canning containers with respect to
their water resistance, chemical stability and other characteristics. Considerably higher performance characteristics are found to have systems containing grafted epoxyacrylates with
carboxyl groups in the side chain as film formers. Dispersions are hardened in the presence
of hexamethoxymethyl melamine at 188C in 60 s. Coatings are distinguished with a high
adhesion to aluminium and stability in hot water.
Carboxyl-containing epoxy oligomers and epoxyacrylates are of interest as potential
film formers for electrophoretic materials for coating the inner and outer surfaces of cans.
Phenol-formaldehyde or nitrogen-containing resins are used as hardeners. Such modified
compositions are used also for coating drawn cans or rolled metal to be used for fabrication
of three-piece composite cans.
Epoxy oligomers modified by polyesters and polyurethanes are used as film formers
of water-diluted materials for coating canning containers. For instance, aluminium and steel
beer cans are recommended to be coated with an aqueous dispersion, which includes
7095% of carboxyl-containing polyester based on trimellitic anhydride and adipic acid
with 530% epoxy dianic oligomer. Upon neutralization with ammonia, the dispersion is
applied to the surface of cans and is hardened for 10 min at 200C. The coating does not
affect the taste of the packaged product.
When producing such compositions, the polyurethane forpolymer is used, which is obtained by the interaction of a mixture of polyester polyol and carboxyl-containing polyol
with polyisocyanate. The latter plays the role of a crosslinking agent. Coatings from these
materials are distinguished by a high chemical endurance, elasticity and adhesion to metal.
Water-diluted materials based on acrylic resins make it possible to obtain coatings
with high durability, light permanence and heat resistance. However, due to the negative
effect on the taste qualities, they are used only for coating the external surface of the container and as coating lacquers for protection of lithographic printing. Such compositions are
produced using alkyl acrylates, methacrylic acid, methacrylates and vinyl acetate.
Coatings based on vinyl materials are distinguished by a high corrosion resistance and
elasticity. However, due to an insufficient heat resistance, they are unsuitable in the cases

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195

when products are subjected to long-time heat treatment. Copolymers of vinyl chloride or
vinylidene chloride with acrylate or other monomers are used the most frequently to produce these compositions.
For protection of the inner surface, use is made of copolymers of methacrylic acid, ethyl acrylate and styrene in a mixture of cyclohexanol and butyl cellosolve containing vinyl
copolymer and epoxy oligomer. Coatings on the basis of water-diluted compositions of this
kind have a high adhesion and render no effect on the properties of canned product.
Aqueous emulsions for coating cans based on polymer of vinyl chloride, ethylene and
acrylic acid have been developed. Copolymerization is carried out in the presence of polyvinyl alcohol, which plays the role of a dispersant. Compositions are used in combination
with melamine-formaldehyde resin for thermosetting coatings.
Aqueous pigmented materials are used for external coating and lithography of cans.
Alkyd, polyester, acrylic or epoxyphenol oligomers are used as film formers in such materials.
Water-diluted materials for coating canning containers are applied on the surface by
rolls, spraying or pouring. The choice of the application method is determined by the type
of container and the process of its fabrication. When producing composite or two-piece cans
by the multiple drawing method, use is made of rolled or sheet material preliminarily painted by any method on a standard equipment. Before formation of cans, the surface of metal
is coated with a layer of lubricant, which facilitates the process of fabrication and protects
the lacquer-and-paint coating from destruction. Two-piece cans produced by the ironing
method are decorated from the outer side and are painted from the inside by spraying. In
this case, the best results are obtained by using double-nozzle sprayers or those with two
mixed nozzles, which enable application of two-layer coatings.

5.9

Compositions with high dry residue and ink powders

An advanced direction of studies in the field of ecologically adequate lacquer-and-paint materials for protection of canning containers is the development of systems with high dry residue. Unlike aqueous compositions, lacquer-and-paint materials with high dry residue wet
the metal support well and do not require special surfactants or other additives. The use of
lacquers with high dry residue has begun from the application of oil-phenolic systems with
dry residue content of 7075%. For instance, lacquers with high dry residue were proposed
for protection of canning containers; as the bonding adhesive, they contain an adduct of an
epoxy oligomer with another oligomer, having amino groups, which perform the function
of a reactive diluter and plasticizer.
Ink powders are a progressive type of ecologically adequate lacquer-and-paint materials; coatings on their basis are characterized by high physicomechanical and protective
properties.
Studies of the use of ink powders for protection of canning containers are carried out
by a number of leading Western companies in the USA, the UK, Germany etc.
However, the use of powder lacquer-and-paint materials for protection of bodies of
canning containers is of limited character due to the high costs of coatings and the complexity of regulating their thickness in the high-speed application process. These drawbacks can
be overcome by using aqueous powder suspensions, which combine the advantages of water-diluted systems and ink powders. Powder suspensions, which make it possible to obtain
coatings of any given thickness, are widely used in the recent years in Japan for protection
of canning containers.

196

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

5.10 Coatings for protection of the outer surface of canning containers


The following materials are used for protection of the outer surface of containers and application of colour or black-and-white patterns on it:
silver or golden primer lacquers intended for creating the background as well as for
improving the elasticity and formability of the whole coating;
white or colour primer enamels for creating the continuous background for the printed pattern;
white, colour and black printing inks intended for protection of a printed image from
mechanical damage, for offset printing on tinplate from flat plates of figures, background
and text in accordance with the reproduced original;
transparent colourless coating lacquers intended for protection of a printed image
from mechanical damage, for giving the coating a gloss, formability and resistance to sterilization in production of canning containers.
The silver background under the pattern applied by printing is created by using colourless transparent lacquers of various grades: AS-548, EP-5190,EP-547; the golden background is created using lacquers EP-559, FL-561, FL-560.
Enamel AS-576 is a suspension of titanium dioxide in a solution of acrylic copolymer
and epoxy resin in a mixture of solvents xylene, butyl acetate and ethyl cellosolve.
White enamel EP-5239 is a suspension of titanium dioxide in a solution of epoxy resin
E-05K, melamine-formaldehyde resin K-421-04, glycerol polyester of sebacinic acid PE-5
and epoxyester EM-34. A mixture of ethyl cellosolve, butanol and xylol is used as a solvent.
Coating lacquers are intended for application over ink impressions; they can be applied both
over preliminarily dried and raw imprints immediately after printing.
Coating lacquers are produced using various resins and their modifications, such as
alkyd, acrylic, epoxy, epoxyester, phenol-formaldehyde, melamine-formaldehyde, polyester. Aromatic hydrocarbons, esters, ketones, alcohols are used as solvents.
To endow the lacquer coating with a gliding ability and strength to scratches, waxes
and silicon additives are introduced into the composition of the lacquer. The table gives the
process parameters of coating lacquers and enamels.
Coating lacquer AS-548 is a solution of acrylic copolymer 5BV in a mixture with epoxy lacquer E-33R in ethyl cellosolve and propylene carbonate. The lacquer is applied on
a roller-type lacquering machine; the thickness of the dried layer is 6 g/m2. The lacquer
coating has a good gloss, hardness, stability to sterilization in combination with protective
primer enamels, for instance, with acrylic enamel AS-576. The coating has the required
elasticity and stability to the stamping of lids and cans with the drawing depth of up to 36
mm.
Lacquer EP-5190 is a solution of epoxy resin E-05K, melamine-formaldehyde resin
K-421-04 and glycerol ester of sebacinic acid PE-5 in a mixture of solvents ethyl cellosolve,
butanol and xylol.
Upon application over dried inks, the lacquer forms a glossy solid coating and is stable
to stamping. Is recommended in combination with enamel EP-5239 for the outer coating of
containers for nonsterilized products.
Printing of labels directly on metal containers as compared with pasting paper labels
significantly increases the quality of the design of the container and reduces its cost 1.82.6
times.
Formulations of new highly efficient lacquer-and-paint materials for printing on metals and the monitored technological process of their application have been worked out. The

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development of rapidly setting materials and technological processes of their application


considerably reduces the costs and increases the quality of printing on metals (Table 5.6.2).
Table 5.6.2 Characteristics of lacquers and coatings.
Material

Viscosity by VZ-4
at 20C

Drying regime,
C

Thickness of
coating, m

Field of
application

Lacquer AS-548

80120

1215 min at
70180C

56

Lacquer EP-5190

5070

1518 min at
170175C

Enamel AS-576

100140

1215 min at
150160C

1518

Enamel EP-5239
white

110180

1518 min at
150160C

1518

Lacquering of ink
imprints for
canning containers
Lacquering of ink
imprints for bodies
of nonsterilized
containers
Bodies of
composite cans,
stamped cans
(diameter up to 36
mm), can lids
Bodies of
nonsterilized
containers

clear

Note: Content of volatiles in the film is from 45 up to 58%.

The technological process of producing an offprint on the metal surface includes three
stages: application of the primer film; printing of an image on the primer film; coating lacquering of the offprint. Formation of lacquer-and-paint films at each of these stages is done
at high temperatures up to 180C for a prolonged time of up to 20 min in large-sized drying
furnaces of up to 10 m in length with large energy intensity up to 1000 kW.
The printing sheet metal is used to fabricate containers for various purposes. The largest thermal, mechanical and hydrothermal impacts to which an offprint on metal is subjected occur in the fabrication of one-piece canning containers. Lacquer-and-paint materials
used to produce an offprint on metal should be stable to these impacts and possess a set of
high adhesion, physicomechanical, waterproof, technological, optical and economic parameters. A number of essential performance properties of lacquer-and-paint materials are
determined not only by the quality composition but also depend significantly on conditions
of their formation. In this connection, the correct protocol of the technological process for
metals is of no less importance as compared with the composition of lacquer-and-paint materials. Most of the recommended compositions for printing on metals do not possess the
set of required properties. They are characterized by a long setting time of 1040 min at
temperatures of 120200C. Many of them become yellow or hydrolyzed, others are not
satisfactory by their mechanical and adhesion properties, which can change depending on
the setting conditions. Due to the multicomponent nature of the recommended materials for
printing on various metals the process of their setting on the offprint is very complex and
is insufficiently studied.
In printing production, two drastically different methods of film formation in printing
on metals are used, such as the removal of solvent and other low-molecular-mass components from the ink and film formation to form a three-dimensional network. Printing inks
for metals are set on the offprint as the result of oxidative polymerization of plant drying

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

oils, natural and synthetic drying oils. For setting primer and coating lacquer-and-paint materials, both hardening methods can be used, i.e., polymerization and polycondensation in
combination with the evaporation of solvent.
To accelerate the processes of film formation of lacquer-and-paint materials on an offprint, various types of irradiation are used thermal, infrared, ultraviolet, electronic the
most widespread of which for printing on sheet metal is the method of thermal intensification. Intensification of the setting of materials in printing on metals requires the use of expensive equipment and a large consumption of thermal energy. About 25% of all production
expenses are used for setting the printing.
A major problem in the considerable improvement of printing-on-metal technologies
is the development of a set of rapidly setting lacquer-and-paint materials and a scientifically
grounded regimes of priming, printing and coating lacquering.
Owing to the specific feature of the technological process, the printing is carried out
not on metal, but on the priming layer, the base of which is a polymer film former. This
technological feature is considered as a prerequisite for constructing the printing ink, whose
setting on the offprint should be performed as the result of the interaction of its components
with the priming film. The basic requirement to the priming film is its high permeability
with respect to the solvent of the printing ink.
Priming compositions were developed based on resin PMK-5, which is a linear amorphous copolymer of butyl methacrylate and methacrylic acid. Modifying additives used
were epoxy resins ED-8 and ED-20, n-tert-butyl-phenol-formaldehyde resin 101l, polyalumophenyl syloxane representing a lacquer of grade KO-810. The compositions were distinguished by ratios of these components. The coatings consisting of 7.5% BMK-5 and
2.5% ED-8 had the optimal properties. As a solvent, the lacquer compositions used a mixture of ethyl cellosolve and butyl acetate at a ratio of 1:1.
Priming films of lacquer compositions of about 10 m thick were formed on supports
at three temperatures of 160, 180 and 200C within the time interval of 1120 min. Destruction of splices was performed on a tensile tester at a displacement rate of the lower
clamp of 30 mm/min. The measurement of adhesion strength was carried out by the method
of shear, which makes it possible to use supports used directly in printing and corresponding
to the conditions of force impact on the film in stamping. In adhesion strength studies, hot
dipped tinplate GZhK-25 fabricated from low-carbon steel band coated with tin on both
sides was used as a support.
Printing inks with the diffusion mechanism of setting on the priming film have been
developed; their basis is a lacquer composition of copolymer BMK-5. The regularities of
migration of free plasticizers based on esters of o-phthalic acid and from solutions of phenol-formaldehyde resins to priming films, as well as the kinetics of ink setting on priming
films of various compositions have been studied. o-Phthalic esters of various compositions,
such as dimethyl phthalate, dibutyl phthalate, dioctyl phthalate have been studied. These
plasticizers are characterized by the largest diffusivity.
Phenol-formaldehyde resins, such as F-60 based on para-tert-butyl phenol and formaldehyde; E-12 based on diphenyl propane and formaldehyde; FT-1 based on para-tert-butyl phenol, diphenyl propane and formaldehyde; modified by various compounds, were
chosen as the film-forming basis of the compositions of printing inks. The absorption kinetics of free phthalates by the priming film of lacquer AE-1 has an exponential character,
and the diffusion increases in the series of the plasticizers dioctyl phthalate, dibutyl phthalate, dimethyl phthalate. The character of the regularity of absorption by the priming film
of phthalates from solutions of resins and the ratio of the diffusion activity between

CHAPTER 5

199

phthalates remain the same as in the case of free phthalates. The studied regularities are the
basis for developing formulations of printing inks with the diffusion mechanism of setting.
The setting rate on epoxyacrylic and epoxyphenol priming films is considerably lower
when using materials and inks based on dioctyl phthalate F-60 as compared with acrylic
priming lacquer AE-1. This is due to the lower permeability of these materials determined
by the significant differences in the structure-formation mechanism in the formation of
films. With these regularities in mind, a mechanism of setting printing inks on priming films
has been proposed.
Owing to the diffusion of plasticizer to the priming film, a solid film of the printing
ink is formed on the surface of the priming film; this solid film is adhesionally bound to the
priming film. The strength of the adhesion bond is determined by the interaction of free
functional groups, available on the surface of the films. The largest adhesion strength is observed in films of the printing ink and the priming lacquer AE-1, as by the moment of printing the film there occurs a partial formation of a three-dimensional structure. Owing to this,
carboxyl groups of BMK-5, which were not consumed totally, interact chemically with the
hydroxyl groups of phenol-formaldehyde resin F-60, and their macromolecules preserve
the capability of intensive mutual diffusion. Studies of the effect of the printing and finishing processes on the adhesion strength of priming films have been carried out. The priming
film, applied to metal and formed in the process of the first technological operation, experiences various effects of the subsequent technological operations. In this connection, the
effect of such factors as the action of printing inks and coating lacquers, deformation rate
and value of deformation of the priming filmmetal system has been studied. Objects of
study were the following: acrylic lacquer AE-1, epoxyacrylic enamel AS-576, epoxyphenol
lacquer EP-547 and alkyd priming enamel, as well as alkyd inks the basis of the bonding
adhesive of which is F-60 with dioctyl phthalate, coating epoxyacrylic lacquers AS-548, as
well as coating systems from Germany and Japan.
The general regularity of the effect of an ink is a decrease of adhesion and strength, an
increase of the ultimate relative elongation of priming films. A depletion of these characteristics is observed in the series of priming materials AE-1, AS-576, EP-547. A decrease
of the adhesion and strength parameters is observed within the range of 1419 down to
710%; herewith, the relative elongation increases by 718%. The change of these parameters correlates with the permeability of priming films with respect to the solvent. The
mechanism of change of the properties of priming films during the impact of solvent or plasticizer on them is the predominant adsorption of the liquid phase on the surface of metal
and the simultaneous plastification of the bulk of the film. The adhesion strength of priming
films in combination with epoxyacrylic lacquer AS-548 increases especially significantly;
herewith, the adhesion strength of the priming film of lacquer AE-1 increases under the action of the coating lacquer, having one film-forming base, which is used for creating a set
of rapidly setting materials.
An increase of the adhesion strength of priming films occurs owing to the diffusion of
the film-forming components of the coating lacquer through them with the solvent, which
at high temperature contributes to the increase of the concentration of reactive groups on
the surface of the support. These groups can be sorbed on the surface of the support to form
intermolecular hydrogen bonds also by way of iondipole interaction of polymer molecules
with the surface groups of the passivation film of metal.
The results of studies of the effect of film-forming and hydrothermal-treatment conditions on the adhesion and physicomechanical properties of compositions made it possible
to develop formulations of priming lacquers based on acrylic copolymers, as well as rapidly

200

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

setting acrylic priming enamels and a rapidly setting coating lacquer on the same filmforming base.
The regularities of the studies of the diffusion properties of the priming layers and dissolving plasticizers enabled the development of printing inks of a new type with the diffusion setting mechanism. On this basis, special purpose inks have been developed, for
printing on metals and ready-prepared items from metal and glass. A feature of the developed compositions is that at the initial stage of film formation, simultaneously with the
evaporation of the solvent, an adsorption layer is created; further on, the reaction of hardening proceeds in the bulk of the films and on the surface of metal to form a three-dimensional structure. The setting rate of inks is determined by the rate of solvent diffusion from
resin to the priming film; an increase of temperature sharply increases the rate. The chemical nature and supramolecular structure of the priming film has a significant effect on the
ink setting rate. An increase of the extent of crosslinking of molecules and a rise of density
of packing of supramolecular formations decrease the permeability of priming films with
respect to phthalates, which reduces the ink-setting rate.
Inks set on priming films by the oxidative polymerization mechanism cause no change
in the adhesion and physicomechanical properties of priming films. Inks containing dioctyl
phthalate decrease adhesion and tensile strength of priming films and increase their ultimate
relative elongation. These regularities in the change of properties of priming films depend
on their permeability with respect to the solvent. However, they do not lead to a critical
change of the performance properties of priming films. Coating lacquers containing free
functional groups increase the adhesion strength of priming films.

6
6.1

Structure and Properties of


Compositions for Protection
of Canning Containers

Ways of improving the protective properties of coatings

Despite the broad range of materials for protection of canning containers, most lacquers
used at present are produced on the basis of epoxyphenol oligomers. However, the diversity
and complexity of the technological processes of fabricating modern types of canning containers, various sterilization regimes of canned products, high requirements to the terms of
their storage compel researchers to search for ways to improve the properties of epoxyphenol compositions. Work is under way mainly in two directions: chemical modification
of particular components of epoxyphenol compositions, mainly phenol-formaldehyde
oligomers, and modification of epoxyphenol compositions by various additives.
To improve the physicomechanical characteristics of phenol-formaldehyde oligomers
and coatings on their basis, these oligomers are modified and plasticized. The modifier for
resol oligomers is chosen of such a structure, so that to ensure the chemical interaction of
the components of the phenol fragment by the hydroxyl and methylol groups.
Phenol-formaldehyde oligomers (PFO) on the basis of glycerol esters of parasubstituted phenols, which contain no free phenol hydroxyl groups, are known. In this case, coatings have high adhesion properties and elasticity.
Of great commercial importance is etherification of methylol groups by unsaturated
fatty acids or high-molecular-mass polyesters containing hydroxyl and carboxyl groups, as
well as by unsaturated, e.g., acrylic and methacrylic, acids. A significant effect of plastification is achieved by introduction of long-chain polyoxy compounds into the structure of
PFO. However, the chemical endurance of coatings on their basis is reduced in this case.
The most widespread way of increasing the elasticity of PFO is their etherification by
alcohols, mainly n-butyl and isobutyl alcohols. Exactly these oligomers are used in epoxyphenol compositions for protection of canning containers. Epoxy-phenol coatings based
on butanolized PFO possess a set of such valuable properties as high chemical endurance
and elasticity, determined to a great extent by the level of PFO butanolization. Coatings
with a high resistance to stamping can be formed from lacquers with etherified phenol-formaldehyde oligomer with a molecular mass of 250500, containing 6.011.0 wt. %
methylol groups and 18.032.9 wt. % etherified groups.
A no less efficient way to improve the protective properties of coatings is structural
modification of initial epoxyphenol compositions by various additives, in particular, by
other oligomers. It has been shown that introduction of oligourethane triisocyanate or

202

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

oligodieneurethane isocyanate in the amount of 0.120.32 wt. % as a crosslinking agent to


the composition based on epoxy and butanolized phenol-formaldehyde resin leads to an increase of elasticity, adhesion and resistance of coatings to the action of organic solvents.
To increase the adhesion strength and especially stability of coatings to sterilization, a modifying additive the product of interaction of epoxy dianic oligomer with a molecular mass
of 5001100 and monopropargyl urethane taken at a molar ratio of 1:(0.21.0) is introduced to the epoxyphenol composition.
Positive results were obtained in modification of commercial lacquer EP-5118 by special additives containing various functional groups (amine, hydroxyl, cyan etc.). The composition obtained in this case forms coatings with internal stresses reduced 25 times as
compared with films from the initial lacquer; high chemical endurance in model food media, as well as increased stability to stamping; the amount of rejects in this case is reduced
by 2030%.
Introduction of low-molecular-mass condensate of fluorinated organosilicon compounds with alkoxylyl groups into compositions makes it possible to obtain coatings for the
internal surface of containers, which prevent deposition of dairy products, oils, vinegar etc.
poured into the containers.
Hardening of epoxy resins by phenol-formaldehyde condensates is accompanied with
a number of reactions, in particular, interaction of methylol and butoxyl groups of phenol
condensate with epoxy and hydroxyl groups of epoxy resin, affecting the quality of the final
product. Therefore, the choice of the optimal ratios of the components and hardening regimes of compositions presents significant problems and is mainly performed empirically.
According to the literature data, acid-resistant coatings are produced using highmolecular-mass epoxy resins with molecular masses above 2500 and alcohol-soluble
resols, for instance, phenol and 1-cresol, both butanolized and nonbutanolized. Novolac
resins and 100% reactive resins can be used as phenol resins. Hardening of epoxyphenol
compositions proceeds better upon addition of 12% phosphoric acid; herewith, epoxyphenol lacquers dry at 180200C for 2030 min. To increase the quality of epoxyphenol
coatings, it is recommended to warm up the mixture of resin solutions preliminarily at
100150C.
The possibility of modifying epoxy resins with phenol-formaldehyde condensates has
been studied, and the properties of coatings on their basis have been investigated.
Low-molecular-mass resins E-40 and E-41, medium- and high-molecular-mass
epoxides E-44 and E-49, as well as resins E-15 and E-05, were used.
Modified and nonmodified resol resins cresol-formaldehyde resin K-212-01, 100%
phenol-formaldehyde resin, phenol-formaldehyde butanolized condensate modified by
Chinese wood oil, as well as xylenolphenol-formaldehyde butanolized resin and maximally
butanolized phenol-formaldehyde condensate were used as phenol-formaldehyde resins.
It has been found that all the above epoxyphenol compositions form water-resistant
coatings. Only coatings with a high-molecular-mass epoxy resin in the amount of no more
than 40% proved to be acid-resistant. Coatings on the basis of low- and medium-molecularmass epoxy resins proved to be non-acid-resistant.

6.2

Effect of the nature of the support on the structure and properties of


coatings

When choosing lacquer-and-paint materials for protection of canning containers, it is


necessary to take into account not only the properties of polymer materials themselves, but

CHAPTER 6

203

also the characteristics of the metal support. This is explained by the fact that the structure
and properties of the polymer coatings formed depend significantly on the nature of the
solid surface and on their thickness. The effect of the support is especially significant at a
small thickness of the coating (46 m) for canning containers.
It has been shown by example of epoxyphenol lacquer EP-547 and supports from electrolytic tinplate (EZhK), chrome-plated steel (KhZhK), aluminium anodized alloy AMG-2
that the microhardness of coatings essentially depends on their thickness and nature of the
support.
The experimental data obtained indicate the predominant influence of the nature of
supports as compared with the microgeometry of their surface (the character of the distribution and size of defects) on the properties of coatings formed on them. Coatings applied
on KhZhK have greater values of hardness, gradient of its change in particular layers by the
thickness of the film and the strength of the adhesion bond as compared with coatings applied on EZhK and AMG-2. This is due to the differences in the size of structural elements,
in the density of their packing, as well as in the morphology of supramolecular structures,
which differ depending on the nature of the support and thickness of coatings. It has been
found that macromolecules of the phenol-formaldehyde components are sorbed from the
lacquer mixture predominantly on the surface of KhZhK and AMG-2 in the process of hardening on the surface of the support, thus forming the structure of the network framework,
whose cells are filled mainly with the epoxy component. On the contrary, in coatings from
EZhK the basis of the structure is made by the epoxy oligomer with the phenol-formaldehyde component evenly distributed in it.
When the thickness of the lacquer layer is increased, coatings on KhZhK and AMG-2
approach those on EZhK by their structure and properties.
The results obtained indicate that a harder and stronger coating with lacquer EP-547
on KhZhK is more stable to the action of aggressive media as compared with coatings on
EZhK, but is less stable to impact loads in stamping as the result of layer-by-layer inhomogeneity determined by the hardness gradient.
With account for these results, protective lacquer compositions should be chosen for
particular types of metal, used to produce canning containers, and the composition of
canned product.

6.3

Structure formation in solutions of epoxyphenol compositions and


the properties of coatings

The results of studies of chemical transformations occurring in fabrication and hardening


of epoxyphenol systems are contradictory and have not been studied sufficiently.
It is pointed out that the reactions of epoxy groups proper, considering their minor content in a real composition, do not contributed significantly to the formation of the molecular
structure and properties of a polymer. Presumably, the greatest role is played by the reactions of the functional groups of phenol-formaldehyde oligomer, of partially butanolized
resol type on the basis of phenol, and substituted with phenol (-resol, n-tert-butyl phenol
etc.). The kinetics of the reactions was studied by the methods of isothermal calorimetry
and chemical analysis, as well as IRS and NMR.
Interaction of PFO and EO during the hardening of compositions occurs by methylol
and butoxyl groups of PFO with secondary hydroxyl groups and o-hydrogen atoms of phenyl cycles of EO.
It is assumed that the instable quality of coatings is due to dissimilar chemical

204

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

endurances of films when using different batches of epoxy oligomer. The low chemical
endurance of coatings is related in a number of works to an insufficient crosslinking when
using different batches of epoxy oligomer.
These regularities are explained by the association of epoxy oligomer in solution. To
decrease the extent of association of epoxy oligomers, use is made of better-quality solvents, which leads to a greater density of the polymer network.
An indirect characteristic of the quality of solvent and the extent of associations is considered to be the critical concentration of associate formation. It is determined using rheological methods.
It has been found that for phenol oligomer the critical concentration in ethyl cellosolve
is two times higher than that for epoxy oligomer. It is assumed that the main contribution
to the formation of associates is made by molecules of epoxy oligomer.
A decrease of the extent of association of epoxy oligomer in solution contributes to a
more even distribution of the phenol component in it and leads to an increase in the density
of the three-dimensional network. However, this worsens the performance properties of
coatings, internal stresses increase, chemical endurance goes down. This is assumed to be
due to the formation of an inhomogeneous defect structure.
The increase of internal stresses contributes to the destruction of coatings in stamping
of workpieces of canning containers.
To improve the performance properties, it is customary to perform the preliminary
forcondensation by heating the mixture of solutions of oligomers in ethyl cellosolve for several hours. However, the mechanism of the occurring physicochemical processes in solutions of mixture compositions and coatings on their basis has not been studied.
Using the method of electron microscopy, it has been found that a homogeneous globular structure is formed in coatings from forcondensates, and the size of structural elements
decreases from 500 to 50 nm.
To elucidate the case of this phenomenon, the method of light scattering was used to
study the features of structure formation in solutions of epoxyphenol compositions depending on the forcondensation conditions.
As initial components, use was made of epoxy dianic oligomer E-04Kr and butanolized phenol-o-cresol-formaldehyde oligomer FKoF-4.
Comparing the parameters of the chromatographically determined molecular-mass
distribution of oligomers and the molecular-structural parameters of their solutions, one can
assume the existence of particles in the form of associated molecules in solutions. Close
values of these parameters testify to a sufficiently narrow distribution of associates by mass.
Studies of the structure of forcondensate solutions has shown that the mass of particles
present in solution decreases in the course of forcondensation to reach a minimum in 1 to
1.5 h. Further on, as the duration of the heating increases, the mass of particles grows. A
change of the mean radius of inertia of particles also corresponds to this change of mass.
The thermodynamic characteristic of the affinity of the solvent to polymer is determined by the value of the second virial coefficient. Its negative value, obtained for solutions
of the initial epoxy and phenol-formaldehyde oligomer, indicates a weak oligomerethyl
cellosolve interaction. An increase of this coefficient with the duration of forcondensation
increasing is, evidently, a consequence of an improved compatibility of the components in
the process of forcondensation.
It follows from the electron-microscopy data on the change of the average size of the
structural elements in coatings depending on the forcondensation time that this regularity
is nonmonotonic and has an extremum at an optimal forcondensation time, to which the

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205

smallest size of the globular structures corresponds.


From comparison of the data on the effect of the forcondensation time on the structure
of solutions and coatings, it follows that the character of the change of size of structural elements is the same both in the liquid phase and in coatings. Higher physicomechanical and
performance parameters correspond to the smallest size of the structural elements.
The method of light scattering was used to study the effect of the moment of introducing orthophosphoric acid as a structure former on the properties of epoxyphenol compositions. The role of the catalyst on the structural parameters of forcondensates was studied in
solutions of ethyl cellosolve with the initial concentration of 0.4 wt. %. Forcondensation
was carried out at 120C for 1.5 h.
It follows from the data obtained that forcondensation in the presence of orthophosphoric acid leads to an increase by almost an order of magnitude of the mass of associates
as compared with solutions without a catalyst.
The data obtained using the light-scattering method made it possible to establish some
features of structure formation in the process of forcondensation in solutions of epoxyphenol compositions. However, the regularities for diluted solutions of compositions established using this method should have been checked in concentrated solutions.
Structural features of compositions determine their optical properties, which depend
on the transparency and refractive indices of mixed components, as well as the extent of
their dispersiveness. However, the close values of the refractive indices of solutions studied
(for epoxy oligomer 1.416 and for phenol-formaldehyde oligomer 1.409) provide for the
transparency of the mixture irrespective of its morphology in the entire range of compositions, exclude the possibility of assessing the structure of the epoxyphenol composition by
controlling its optical properties.
For this reason, the rheological properties of concentrated solutions of initial oligomers and epoxyphenol compositions, depending on conditions of their formation, were
studied, which reflect the occurring structural transformations.
The character of the rheological curves suggests that within concentrations up to 20%
the solutions of initial oligomers and compositions on their basis are Newton-type systems,
i.e., the dependence of viscosity on shearing stress is a straight line parallel to the abscissa
axis.
As the concentration of solutions is increased up to 4050%, their viscosity is observed to rise; there are some changes in the character of the rheological curves, on which
an area of structural viscosity appears. However, the absence of a region of constant viscosity indicates that in this area of concentrations solutions are weakly structured systems,
in which the number of contacts between structural elements is insignificant.
Evidently, in this case the major part of intermolecular bonds is used to form primary
aggregates of macromolecules, and only an insignificant part of them is consumed for the
bulk structuring of the system. Already at small loads there is the rupture of bonds involved
in the formation of the three-dimensional network and the breakdown of the structure to the
primary associates of macromolecules.
Thus, in the range of working concentrations of solutions from 15 upto 40% the rheological parameters of epoxyphenol compositions are characterized mainly by the lowest
Newton viscosity, whose value is determined predominantly by the size of the primary
structural elements.
The rheological characteristics of solutions of epoxyphenol compositions change similar to the way they change in solutions of individual oligomers. Apparently, the character
of structure formation and peculiarities of interaction of oligomers with the solvent in the

206

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

mixture composition does not change.


The regularities in the character of interaction of the epoxyphenol-composition components depending on the conditions of their compatibility is well traced in studies of the
rheological characteristics of the composition-dependent solutions assessed by the change
of the relative viscosity of the system. The curve of the viscositycomposition dependence
obtained for a mechanical mixture of epoxy and phenol-formaldehyde oligomers goes
above the additive line, which indicates a more intensive interaction in the mixture as compared with solutions of individual oligomers. This deviation is much more pronounced for
solutions of forcondensates.
The viscosity of a composition changes nonmonotonically depending on the forcondensation conditions and reveals a minimum in the point corresponding to the smallest size
of structural formations. Evidently, an improvement of the thermodynamic compatibility
of the components in the process of forcondensation and a decrease of the size of the structural elements in the solution at a certain warmup time lead to a decrease of the system viscosity. The subsequent increase of the extent of association and the worsening of the
interaction of oligomers with the solvent are accompanied with an increase of viscosity.
As the molecular mass of epoxy oligomer is increased, the regularities in the change
of the rheological properties are preserved; however, the optimal time of warming up the
composition slightly increases.
To establish the relationship between the processes of structure formation in solutions
of epoxyphenol compositions and in the formation of coatings on their basis, as well as to
study the effect of the supramolecular structure of the coatings on their properties, the structure of films was studied by the method of electron microscopy. It has been found that coatings from a mechanical mixture of epoxy oligomer and phenol-formaldehyde oligomer
reveal an inhomogeneous defect structure from large structural elements of 500700 nm in
size, which form a sparse three-dimensional network. A preliminary warming-up of the
composition contributes to an increase of the structural homogeneity of films and a decrease
of the size of supramolecular formations; the more homogeneous structure is formed in
coatings from forcondensates obtained at an optimal warmup time. The size of globular formations in such coatings is 5070 nm. An increase of the forcondensation time as compared
with the optimal time leads to the aggregation of structural elements and the formation of
large associates 0.20.3 m in diameter.
The structural features of films determine the value of vapour permeability and the extent of their swelling in butyl acetate. The lowest value of vapour permeability corresponds
to films with the finest globular structure. The extent of hardening of coatings in this case
is at its maximum, so they are less prone to swelling. An increase of the size of structural
elements with the forcondensation time greater than the optimal value leads to a rise of vapour permeability of the films and a decrease of the extent of their hardening.
Comparison of the data of structural transformations in solutions of epoxyphenol compositions and the results of structure studies suggests that the regularities of structure formation in the liquid phase are well consistent with the structural changes in the formation
of coatings. Evidently, the formation of an ordered structure of the coatings is a consequence of an increased structural homogeneity and an improvement of compatibility of
epoxyphenol-composition components in forcondensation in an optimal temperaturetime
regime.
Structural features of coatings are closely related to the value of internal stresses,
which, in turn, has an effect on the main performance properties of the coatings, for instance, adhesion and mechanical stress. The kinetics of change of internal stresses in the

CHAPTER 6

207

formation of coatings and the effect of various physicochemical factors on their value,
including the regime and compatibility of components in production of epoxyphenol
lacquers, have been studied.
The kinetics of change of internal stresses in the formation of coatings from epoxyphenol compositions depending on the conditions of matching the initial components has
been studied; it has been found that the rate of increment and the value of internal stresses
depend on temperature and time of forcondensation.
The ultimate values of internal stresses in coatings from a mixture of epoxy oligomer
and phenol-formaldehyde oligomer not subjected to forcondensation settle in 0.51.0 h
after the onset of hardening, and subsequently remain invariable. Forcondensation leads to
a significant acceleration of the coating formation process, which is completed in 1520
min.
The value of internal stresses decreases with the increase of the warmup time of the
compositions up to 11.5 h. The further increase of the forcondensation time increases the
internal stresses. Similar regularities in their change are also observed in the formation of
coatings from forcondensates obtained at lower temperatures; however, in this case the minimum shifts towards larger warmup times and the value of the ultimate stresses slightly increase. An increase of the forcondensation temperature above 120C also leads to the
increment of internal stresses in hardened films.
Comparative characteristics of coatings from epoxyphenol compositions with ratios of
the components E-04Kr : FKoF-4 = 80 : 20 wt. % depending on the heating time are given
in Table 6.1.
Table 6.1
Duration of
heating, h

Content of gel
fraction, %

0
0.5
1.5
6.0

76.1
78.0
80.4
67.2

Internal stress,
Tensile
MPa
strength, MPa
4.55.0
3.53.8
2.8
4.24.5

6.8
7.3
8.0
7.1

Chemical endurance in 3%
CH3COOH at 100C, h
3.5
3.5
4.5
3.5

Comparison of the results of structural studies with the data of the change of the properties of coatings shows that the increase of the structural homogeneity of films in forcondensation in an optimal regime contributes to the increment of the strength and protection
characteristics of the coatings, as well as to a decrease of internal stresses.
The correct choice of the temperaturetime conditions of forming the coatings makes
it possible to create an optimal supramolecular structure, which provides for high performance parameters.
The effect of the hardening regime of epoxyphenol coatings on their structural features
and physicomechanical characteristics was studied. Coatings based on epoxyphenol compositions with the ratio of components E-04Kr with the average molecular mass of 5 103
and FKoF-4 equal to 80:20, heated under optimal conditions at 120C for 1.5 h, were
formed within the temperature range of 200400C. The coating formation process was
studied by the kinetics of change of internal stresses in the process of their hardening. It was
found that the hardening rate increased significantly with the formation temperature rising.
At 300C, this process takes several seconds; herewith, the dependence of ultimate values
of internal stresses is of extremal character and reaches its highest value at 250300C.

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

The dependence of internal stresses on hardening time is also nonmonotonic. Upon


reaching a maximum, they decrease the larger, the higher the temperature is. The completeness of coatings hardening was controlled by the content of gel fraction after extraction in
Soxhlet extraction apparatus, because the theoretical calculation of the crosslinking density
is difficult to make for the systems studied due to the high molecular mass and functional
polydispersity of the components. It has been found that the most complete hardening of
the system is achieved at a temperature of 250300C.
The results of the differential thermogravimetric analysis have shown that in the temperature range of 280300C the polymer is subjected to thermodestruction; with the content of epoxy oligomer in the composition increasing the temperature of the onset of thermodestruction decreases.
It follows from the electron-microscopic studies of the structure of coatings hardened
at various temperature regimes that coatings hardened at 200250C have a homogeneous
structure with the size of supramolecular formations of 5070 nm. Herewith, the features
of structure formation correlate with the structure observed in the solution of epoxyphenol
compositions in the process of forcondensation.
An increase of the coating formation temperature leads to the emergence of more complex structural forms of various morphologies; herewith, globules and associates of
globules are distributed unevenly in the general mass of the film.
Intensive destruction processes at temperatures above 300C lead to the rupture of
chemical and physical bonds to form low-molecular-mass products and the formation of an
uneven network from chain-type structures; herewith, the physicomechanical and protective characteristics worsen (Table 6.2).
Table 6.2
Hardening regime

Characteristics of coatings

Temperature,
C

Duration

Content of gel
fraction, %

Internal stress,
MPa

Chemical endurance in 3%
CH3COOH at 100C, h

200
250
300
390

20 min
10 min
2 min
40 sec

75.6
80.4
81.1
49.5

2.83.0
3.53.8
3.84.0
2.52.8

4.0
4.5
4.5
3.5

Analysis of the obtained results suggests that the warming up of a mixture of oligomers
at 120C contributes to the formation of a homogeneous ordered structure at the coatinghardening temperature of 250300C.

6.4

Dependence of the properties of can lacquers on the structure of


phenol-formaldehyde oligomers

The hardening regime of coatings based on epoxyphenol lacquers depends on the type of
metal, the support. For tinplate, it is 210C for 1015 min; for aluminium, 360390C for
3040 sec. In the latter case, owing to the strong thermal shock, the properties of coatings
worsen in the process of hardening. With account for this, a wide range of epoxyphenol lacquers, for instance, EP-527, EP-547, EP-5118, etc. are manufactured by Russian industry;
mainly lacquer EP-5118 is used, which does not always provide for the required properties

CHAPTER 6

209

of the coatings, which should combine the high chemical endurance to sterilization in solutions of tartaric and acetic acids and sodium chloride and withstand stamping.
The phenol-formaldehyde component imparts chemical endurance to coatings based
on epoxyphenol compositions, as well as determines the stability of coatings at stringent
hardening regimes 360390C for 3040 sec.
It has been found that the properties of coatings are significantly affected by the characteristics of phenol in synthesis of phenol-formaldehyde oligomer, such as molecular
mass, molecular-mass distribution, content of methylol groups, extent of their butanolization. The currently existing technology for production of these oligomers does not make
possible the directed regulation and qualitative assessment of their characteristics. Using
this process, a large amount of waste waters is produced up to 3000 kg/t; herewith, commercial oligomers contain no more than 10% (by weight) of butoxyl groups.
A new technology of producing phenol-formaldehyde oligomers has been developed.
The process makes it possible to separate in time the reactions occurring in their synthesis
(hydroxymethylation of phenol, polycondensation of methylol derivatives of phenol, etherification of methylol groups) and to decrease the amount of waste waters to no more than
120 kg/t.
The process developed was used to synthesize butoxylated oligomers on various phenols: phenol proper, cresols, xylenols and diphenylol propane. The latter were tested in
epoxyphenol lacquers for internal protection of canning containers.
The choice of this phenol was due to a number of reasons:
use of phenol with the hinged link contributes to the increase of the physicomechanical properties;
high functionality of diphenylol propane with respect to formaldehyde makes it possible to produce oligomers with a sufficiently high content of butoxyl and free methylol
groups;
decrease of the relative share of methylol bridges in these oligomers as compared
with oligomers based on other phenols makes it possible to increase the resistance to
thermal shock.
A new type of high temperature-hardened epoxyphenol compositions based on o-alkylated phenol-formaldehyde oligomers for fabrication of rapidly drying lacquers to form
coatings with high physicomechanical and protective properties has been developed. These
oligomers of grade OAPFO are characterized by a low reactivity of methylol groups at room
temperature and a practically unlimited stability in storage. After 1224 months of storage
they do not change their properties, whereas in other phenol oligomers the formation of gel
particles and delamination are observed. The reactivity of OAPFO strongly changes with
the rise of temperature, owing to which at temperatures greater than 350C the coatings on
their basis are distinguished by a high degree of hardening, thus providing for a good hardness and thermal stability (Table 6.3).
The effect of the features of structure formation in solutions of epoxyphenol compositions has been studied.
It has been shown that epoxyphenol compositions with OAPFO on the basis of mechanical mixtures are not inferior than and sometimes even exceed coatings based on traditional forcondensates with the component matching regime optimal for butanolized PFO.
Based on the data on the studies of the hardening process of epoxyphenol coatings, a general
scheme of the process has been proposed for OAPFO-based compositions. It has been
shown that the determining reaction in hardening, as in the case of coatings based on

210

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

butanolized phenol-formaldehyde resol oligomers, is the interaction of methylol groups one


with another.
Table 6.3 Optimization of hardening regimes.
Hardening regime
Time, min
60
90
120
15
10
2
40 sec
40 sec

Content of gel fraction, wt. %

Temperature, C

PFO-based coatings

OAPFO-based coatings

100
100
100
210
250
300
360
390

75.6
80.4
81.1

49.5

10.4
12.4
19.8
82.5
83.9
52.1
83.9
88.0

Comparative studies of epoxyphenol coatings, hardened at 360C for 3060 sec,


based on etherified and nonetherified phenol formaldehyde oligomers o-alkylated with
dimethyl sulfate, butyl glycidyl ester and glycilyl ester of higher isomeric carboxylic acids,
as well as commercial oligomer FPF-1 show that coatings based on OAPFO are characterized by a higher adhesion strength, elasticity, chemical endurance and lower vapour permeability as compared with coatings from compositions with butanolized phenolformaldehyde oligomer as the result of the decreased contribution of side reactions.
In the series of epoxyphenol coatings based on those o-alkylated with butyl glycidyl
ester the best set of properties is with coatings with butanolized o-alkylated phenolformaldehyde oligomer synthesized at a phenol : formaldehyde : butyl glycidyl ester molar
ratios of 1.0 : 1.78 : 0.33 and 1.0 : 2.5 : 0.33. In the latter case, coatings have a higher extent
of hardening and low vapour permeability (Table 6.4).
Table 6.4 Properties of epoxy phenol coatings based on forcondensates and mechanical mixtures
of epoxy oligomer and OAPFO oligomer (at ratios 80:20, wt. %), hardened at 360C.
Ratio, mol/mol
phenol

Content, mol/mol OAPFO

Formaldehyde

BGE

Phenol
OH group

CH2OH

CH2 OC4H9

1.78
1.78
2.50
2.50
1.78
1.78
2.50
2.50

0.33
0.33
0.33
0.33
0.50
0.50
0.50
0.50

1.779
1.779
1.659
1.659
0.727
0.727
0.709
0.709

0.908
0.908
1.200
1.200
0.894
0.894
1.200
1.200

0.959
0.959
1.007
1.007
0.946
0.946
1.005
1.005

*mm, mechanical mixture; **fc, forcondensate.

Mn
Fabrication
technique

540
540
620
620
580
580
670
670

mm*
fc**
mm
fc
mm
fc
mm
pc

Chemical
endurance,
points

5.0
5.0
5.0
5.0
3.0
3.0
3.0
3.5

211

CHAPTER 6

For coatings mentioned in the table, the adhesion strength in bending is, in millimeters,
1 (according to a ShG-1 curvimeter), besides coatings from composition 4, for which this
parameter is equal to 3.
Epoxy-phenol lacquers based on diphenylol propane-formaldehyde oligomers with a
high content of butoxyl groups form coatings, satisfying all the requirements imposed on
can varnishes. At any hardening regime, including the rapid high-temperature drying, they
form chemically stable coatings withholding stamping and suitable for fabrication of cans
with the drawing coefficient up to 1.7.
For coatings from lacquer EP-5118 and a composition based on OAPFO, the effect of
the stage of forcondensation on the internal stresses in the formation of coatings was
studied. Forcondensations were shown to contribute to a decrease of stresses in coatings
from lacquer EP-5118; herewith, the forcondensation stage has no effect on internal stresses
and is not required.
Coatings from a composition based on OAPFO without forcondensation are characterized by a higher adhesion strength, chemical endurance in water and acetic acid as compared with coatings from compositions obtained via the forcondensation stage, as well as
by a higher adhesion and stability to stamping unlike coatings from composition EP-5118
(Table 6.5).
Table 6.5 Effect of the forcondensation stage on the properties of epoxy phenol coatings (at an EO
and PFO ratio of 80:20).
Composition

EP-5118 with fc
OAPFO-based without fc
OAPFO-based with fc

Adhesion
strength,
points

Chemical endurance, points


H2O

3% solution of CH3COOH

3
1
2

5
5
4

4
4
3

Stampability,
points
4
5
5

The effect of the ratio of epoxy oligomer and OAPFO on the properties of coatings
was studied. It has been shown that at a component ratio of 80:20, 75:25 and 70:30 the coatings are characterized by the same values of internal stresses. The difference is that at a ratio
of 75:25 and 70:30 coatings harden for 10 sec at 350C, and at a ratio of 80:20, for 1.5 min.
Coatings from compositions with the ratio of 80:20, though they have lower stresses, by
their protective properties and strength are inferior to compositions with the ratio of 75:25
(Table 6.6).
Table 6.6 Effect of the ratio of epoxy oligomer and phenol-formaldehyde oligomer on the
properties of coatings.
Ratio of EP
and OAPFO,
Content of gel
wt. %
fraction,
wt. %
80 : 20
75 : 25
70 : 30

84.0
86.1
81.3

Properties of coatings
Bending
strength,
mm

Adhesion
strength,
points

Chemical endurance, points


H2O

3% solution of CH3COOH

1
1
3

2
1
2

5
4
4

4
5
3

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

The use of novel chemically modified epoxyphenol lacquers makes it possible to significantly reduce rejects in container fabrication, to expand the range of packaged products,
to increase storage times of canned products due to a better protection of the inner surface
of metal stamped containers form the impact of biochemically active media.
The effect of chemical composition and synthesis conditions on the molecular characteristic of PFO was studied. As initial components in their synthesis, use was made of phenol, cresols, n-tert-butyl phenol, 3,4-xylenol and mixtures of phenol with these compounds.
The best results using linear PFO were obtained on the basis of n- and o-cresol-formaldehyde oligomers (Table 6.7).
Table 6.7 Properties of coatings.
Base of PFO
p-cresol
o-cresol
n-TBP
3,4-xylenol
p-cresol
p-cresol
p-cresol
o-cresol
o-cresol
phenol

6.5

Mn of
PFO

PFO CH2OH,
mol

A,
points

280
355
350
375
290
250
290
460
500
490

0.92
0.98
0.98
0.96
0.75
0.90
0.96
1.35
1.48
1.68

1
1
3
2
2

b,

MPa

P108,
g/(cm2 h)

Chemical endurance,
points

3.8
3.1
2.0
2.8
2.5
2.9
3.1
5.0
5.4
6.8

3.0
3.5
7.0
4.5
3.5
3.2
3.0
2.5
2.7
2.0

4.2
3.8
1.5
2.4
3.5
4.5
4.5
4.0
4.0
4.0

Fields of application of canning containers and methods of their


modification

Diversification of canning products is accompanied by the improvement of packagings. The


relative share of metal containers increases, as well as that of small consumer containers in
the form of tinplate cans, packagings from combined materials on the basis of aluminium
foil for ready-prepared sterilized and frozen meals.
Sterilized ready-prepared meals and semi-finished convenience products are produced
in tinplate cans of various sizes. They contain several gobbets and by their taste are not inferior than the meals prepared by traditional cooking methods. Before use, they are warmed
up and portioned.
A wide assortment of sterilized ready-prepared meals and convenience foods have
been mastered, for instance, stuffed pepper with meat, stuffed cabbage leaves with meat,
veal with garnish, etc. packaged using metal containers.
Tinplate containers are used for packaging convenience foods, which passed a culinary
treatment and can be used after a small additional processing mixing, addition of spices,
warming-up, roasting. Meat semi-finished products are usually combined with canned vegetable semiproducts.
Tinplate cans are used to package dietary foods, whose output continuously increases.
A ranking place in using this group of packagings is occupied by medicated food products
beverages enriched with pectin, fruit desserts from natural fruit puree apricots, apples,
pears, quince or carrots with addition of sugar syrup. These products are recommended

CHAPTER 6

213

in prophylaxis and therapy of diseases related to the increased content of fats and cholesterol in the blood, chronic coronary insufficiency after infarction.
Metal containers are widely used in production of fruit preserves juices, stewed
fruits, drinks based on fruit syrups, apple concentrates and other fruits with natural aromatizers. Aceptic packagings for tomato concentrate are introduced, as well as special tubes
based on metallized materials.
Traditional types of containers for production of canned food in this country are metal
cans from tinplate and aluminium, as well as glass jars with lids from tinplate, chromeplated steel or aluminium. In the case of glass containers, expenses for transportation and
storage of canned products as well as due to breakage of jars, are much greater. Use of metal
containers decreases the labour intensity and duration of sterilization, increases labour productivity, reduces the requirement in storage facilities.
Production of canning containers in the recent years makes use of advanced materials,
such as aluminium, chrome-plated and aluminized steel instead of deficit tinplate, as well
as materials with a reduced thickness of the tin layer on tinplate.
Protective coatings on rolled metal materials are produced using high-speed lines,
which provide for hardening of the lacquer in several seconds at 350390C. The design
and assortment of produced canning containers have changed. Widely used are deep drawn
cans, welded-seam composite cans, stamped and composite cans from two different metals,
tubes, etc.
Resource-saving technologies and equipment for production of metal containers have
been developed. Machines for fabrication of two-piece aluminium cans provide for the
economy of materials without decreasing the parameters of strength in compression. This
is achieved due to the improvement of the shape of the bottom, which, in turn, makes it possible to decrease the thickness of the walls to 0.28 mm. Based on the use of new equipment,
the extent of the change of can volume in the process of pasteurization is significantly decreased.
Introduction of new types of technological and transport containers, as well as
advanced technologies of their fabrication from preliminarily lacquered aluminium band by
the method of deep drawing impose stringent requirements to the quality of
lacquer-and-paint coatings, especially for its internal protection, and an increase of shelf
life. The major of them are biochemical stability, high strength and elasticity, which provide
for a sharp decrease of internal stresses in the formation of coatings and the impact of mechanical fields in stamping.
Compositions widely used in industry for protection of canning containers are
epoxyphenol compositions based on high-molecular-mass oligomer hardened with
phenol-formaldehyde oligomer EP-5118, modified with a mixture of glyptal and polyphenyl silaxane resin Ko-815. A significant drawback of coatings based on this lacquer are
high internal stresses, small elasticity and low chemical endurance, which hinders their use
in production of one-piece canning containers.
Methods of modifying epoxyphenol lacquers have been developed, which make it possible to increase the resistance of protective coatings to the action of biochemically active
media and mechanical fields in stamping. The modification methods are based on introduction of special texturing agents into compositions.
The object of study were epoxyphenol compositions with the epoxy oligomer and
phenol-formaldehyde oligomer ratio of 80:20, as for commercial lacquer EP-5118. To
make the components compatible, forcondensation at 120C for 1 h was carried out. In the
subsequent mixing, orthophosphoric acid was added as a catalyst, as well as modifying

214

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

agents, containing various functional groups, such as amine, hydroxyl, cyan etc. As the result, a modified composition with higher protective properties and chemical endurance as
compared with the initial composition was developed. The thickness of coatings, stability
to stamping, chemical endurance and internal stresses were studied.
In accordance with technical specifications, the thickness of coatings was determined
by a micrometer gauge and by the weight method; it was 5 mm. The endurance of coatings
to mechanical impacts was assessed in stamping of cylindrical cups 33 mm in diameter with
the elongation coefficient of 0.6 (the ratio of height to diameter) and was expressed as a
percentage of destroyed coating. The chemical endurance of stamped specimens was studied under standard conditions in model media for 60 min at a pressure of 100 kPa (1 atm)
and 120C. It was assessed in points:
5 points lacquer coatings without changes;
4 points the inner surface with barely noticeable changes in the form of separate
strokes or points by the angles of drawing;
3 points insignificant change of colour and gloss, barely noticeable peeling;
2 points change of colour and gloss, peeling, spots of curling of lacquer;
1 points curling of lacquer over the entire surface.
Chemical endurance of lacquer coatings was assessed by the change of electrochemical potential on a potentiostat P-5827 in an electrolytic cell for electrochemical studies
with the determination of the breakdown potential. The specimen was held in solution for
10 min. In the process of polarization, the current density was measured after each 50 mV.
Internal stresses were measured by the photoelastic method (Table 6.8).
Table 6.8 Protective properties of coatings.
Composition
Chemical endurance, points
of lacquer,
3% solution 2% solution 3% solution Distilled
%
of acetic
of tartaric
of sodium
water
acid
acid
chloride

,
mV

Extent of
breakdown
of coatings,
%

b,
MPa

No additives
2.1
3.2
4.5

450
+400
+813
+450

2030
Abrasions
No abrasions
Abrasions

1.0
0.5
0.2
0.4

3/2
4
5/4
4/5

3/2
4/5
5
5

3/2
4/5
5
4/5

3/2
5
5
5

Note: The slashed numbers indicate the limits of measured values for a series of 10 specimens.

It is seen from the table that coatings based on basic commercial lacquers are characterized by a low stability to stamping and protective properties in various media within the
range of 3 and 3/2 points. Chemical endurance of coatings from compositions modified by
organosilicon compounds increased significantly up to 5 and 5/4 points. For modified
coatings, the breakdown potential is significantly shifted to the positive side, the stability
of coatings to stamping increases as the result of the decrease of internal stresses. The supramolecular structure of coatings was studied by the method of electron microscopy; it was
shown that the size of structural elements decreased as the result of modification to 0.4 m.
For nonmodified coatings, larger supramolecular formations of up to 0.85 m in size were
observed. It follows from these data that introduction of a modifier leads to the formation

CHAPTER 6

215

of coatings with an ordered structure.


To improve the performance properties of can varnishes and to impart a high elasticity
to coatings on their basis, they are modified by epoxyesters of various molecular masses.
The properties of coatings based on epoxyphenol compositions from the mixture of epoxy
oligomer E-04kr and phenol-formaldehyde resin FPF-1 at a ratio of 1.5:1 were studied.
The epoxyesters used were synthesized from epoxy oligomers ED-20 with an average
molecular mass of 400; E-44, with a molecular mass1600; E-05k, with a molecular mass of
3000; and oleic acid, taken at an equimolar ratio of 1:1, and in the base of E-05k also at a
ratio of 1:2. The former epoxyesters are monoepoxyesters; the latter, a diester.
The most significant barrier effect for the diffusion of corrosion agents through the
protective film was observed for coatings modified by monoepoxyesters based on the most
low molecular-mass oligomer ED-20 in the amount of 20%.
The effect of epoxyesters on the protective properties of coatings is confirmed also by
the results of the assessment of chemical endurance in sterilization in model media. The
protective action of coatings is determined not only by the barrier properties of polymer
films, but also by the adhesion strength. The results of determining the character of coatings adhesion strength change after sterilization have shown that coatings containing a
modifier based on E-05k have a greater stability of adhesion properties.
The effect of film polarity decrease affecting the diffusion of the corrosion medium
increases with the rise of the concentration of monoepoxyester. This is, evidently, due to
the distribution of weakly polar fatty radicals in the bulk of the polar epoxyphenol matrix.
Studies of epoxy polymers have shown that a decrease of their polarity is accompanied with
a decrease of the sorption of water molecules and electrolyte ions.
By the example of epoxyphenol lacquers EP-547 and EP-547M, it has been found that
a decrease of polarity of coatings using higher-molecular-mass epoxy oligomers leads to an
increased stability at the action of aggressive sterilization media.
When passing from monoepoxyester to diester, the dielectric permeability of coatings
increases. We suggest that this is due to an increase of the volume content of strongly polar
ester groupings, whose dipole moment is 2.5D. Presumably, this explains an increase of the
value of cathodic current in substitution of monoepoxyester (MEE) to diester in compositions based on E-05k. The level of dielectric losses of coatings in the introduction of
epoxyesters increases in all cases because of the rise of mobility of small fragments of sterically structured molecules owing to the plasticizing action of modifiers (Table 6.9).
Thus, introduction of plasticizing epoxyester modifiers into the epoxyphenol composition enhances the mechanical and protective properties of coatings. This effects is more
Table 6.9 Effect of modifiers on the adhesion of epoxy coatings in aggressive media.
Medium

Preservation of adhesion (%) of coatings,


with 20 wt. % modifier
No modifier

Distilled water
3% solution of tartaric acid
3% solution of acetic acid
3% solution of sodium chloride

60
50
70
80

MEE

DE

ED-20

E-14

E-05k

E-05k

100
98
100
100

98
95
95
99

98
98
98
98

100
98
98
100

216

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

pronounced when using low-molecular-mass epoxyesters as modifiers.


The properties of epoxyphenol coatings depend on the structure and optimal ratio of
the functional groups in phenol oligomer. Mixtures of phenol and n-tert-butyl phenol of the
type of FPF-1 within a broad range of values of functional groups, bridging linkages, average molecular masses were synthesized. The range of values in wt. % of oxymethyl groups
was 2.514.6; of butoxymethyl groups, 9.022.0; methylene bridges, from 1.3 up to 5.6;
oxymethyl bonds, from 0.3 up to 4.4; the molecular mass of the oligomers was changed
within the limits of 290650.
It has been found that epoxyphenol compositions based on the given mixture phenols
with the mass fraction of butoxymethyl groups of 913% do not provide for the required
stability of coatings to stamping, at an increase of their content to 1822% the elasticity of
the coatings was significantly improved. An increase of the mass fraction of the oxymethyl
groups from 2.55.6% up to 814% worsens the elasticity and stability of specimens to
stamping.
It has been shown that coatings from lacquer EP-547 on tinplate provide for a relatively high stability to stamping, combined with the acceptable chemical endurance and adhesion. These oligomers are distinguished with a high content of butoxymethyl groups
(1618%) and methylene bridges (3.24.1%) at a comparatively low content of the oxymethyl groups within the range of 6.110% and dimethylene oxide bridging linkages of
1.02.3%. Herewith, the residual content of free phenols in individual specimens was about
8% and had no negative effect on the quality of the coatings.
It follows from these data that variation of the structure of phenol oligomer within sufficiently wide limits of the functional groups and bridging linkages does not make it possible to produce lacquer coatings, which would combine a high chemical endurance with
mechanical properties. When designing compositions, it is necessary to take into account
which characteristics of coatings are preferable for a particular purpose composite or
stamped containers, aggressiveness of the product stored.

6.6

Structure and properties of coatings based on epoxy oligomers

Protective and decorative polymer coatings are distinguished by a diversity of properties


depending on their purpose and performance conditions. Their specific features are that
they are formed as thin films on the surface of solid bodies (rigid and soft supports). Depending on the purpose, polymer coatings should satisfy various mechanical, adhesive,
thermophysical and electrophysical properties, and in some cases also such specific parameters as the sensitivity to a definite radiation range, bactericidal and fungicidal properties,
certain porosity, thermal stability, incombustibility etc. A combination of these properties
is achieved mainly by synthesizing polymers with certain functional groups and chain structure, molecular and supramolecular structure, as well as the result of their physical and
chemical modification.
Depending on the chemical composition of film formers, the nature of the functional
groups and formation conditions, the coatings produced can have a linear, branched and network structure.
The decorative properties of coatings are changed and the protective properties are increased also by adding organic dies, mineral pigments and reinforcing fillers. The properties of coatings can be regulated within broad ranges by their physical modification with
the aim to form a homogeneous structure.
To develop the physicochemical bases of forming polymer coatings, it is necessary to

CHAPTER 6

217

study the peculiar features of structure formation and properties of various types of film
formers, their effect on the specific features of structural transformations at various stages
of polymer coatings and their properties formation.
The process of forming coatings is accompanied with the emergence of local bonds
between the most active groups of macromolecules and other structural elements, and has
much in common with the mechanism of gel formation. When conducting these studies,
special attention was paid to the effect of the nature of the support on the structure and properties of coatings and interphase layers, as well as to the process of their formation. Manifestation of the special properties of the boundary layers, determined by the orienting effect
of the support, particles of the filler or fibrous reinforcing materials, is not restricted by the
bounds of one or several molecular layers, but significantly affects the structure and properties of the coatings on the whole. The specific features of polymer coatings are that they
are formed as comparatively thin films on the supports that adhere well to polymer, so the
surface phenomena play an important role in the formation of their structure and properties.
The structure of coatings from epoxy resin ED-20 obtained on a glass support at 80C
was studied. It has been found that a sharp change in the structure of the layers is observed
in the layers bordering with the support and the air. Away from the border (100200 nm)
the structure of middle layers is stabilized and does not change significantly in passing from
one layer to another. At the interface with the support, the structure was homogeneous and
globular owing to the adsorption interaction of the film former with the surface of the support and a sharply slowed-down mobility of the structural elements. Away from the interface with the support, owing to the increase of the mobility of structural elements, they are
observed to aggregate to form more complex structures up to 100200 nm in size.
The inhomogeneity of the structure of coatings is preserved during their formation at
various supports and under different hardening conditions. Addition of active fillers to the
system increases the inhomogeneity of the structure. The authors studied the structure of
various layers of coatings 200 mm thick from epoxy resin ED-20 formed on a glass support
at 150C. It has been shown that in surface layers bordering the air the polymerization is
the most rapid, and a thin homogeneous structure is fixed, which coincides by its size with
the associates observed in the initial oligomer. The largest aggregation of structural elements, which accompanies the formation of a complex secondary supramolecular structure,
is observed in middle layers of the coatings. The change of the nature of the support renders
a specific effect on the structure of individual layers of the coatings, not eliminating its inhomogeneity by the thickness of the film. From the data on the structure of epoxy coatings,
but formed on block copper, it follows that in layers bordering with the support there occurs
a structure, which reflects the granular texture of the support. In the surface layers, structural elements are observed to aggregate to form more complex secondary structures. At
the introduction of active fillers, in particular 4 wt. % rutile, the structural inhomogeneity
of these coatings is significantly increased.
A substantial feature of polymer coatings is that surface phenomena have a significant
effect not only on the character of the structural transformations, but also on the rate of relaxation processes and the properties of coatings. The retardation of relaxation processes in
the formation of coatings, which is due to local links between structural elements and adsorption interaction of the film former with the surface of the support, is accompanied by a
sharp increment of internal stresses.
Internal stresses are determined by the shrinkage of gels produced in the formation of
coatings; they start to manifest themselves after the coatings are formed owing to the
inhibition of the relaxation processes. In this connection, internal stresses in coatings are

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

affected by the factors determining the rate of the gel formation process. These factors, besides the concentration of the initial solution, also include the effect of the nature of solvent
and various texturing agents.
One of the ways of decreasing internal stresses is regulation of the relaxation processes
at the polymersupport and polymerfiller interfaces, which enables creating a homogeneous ordered structure in coatings.
Internal stresses emerging in the formation of coatings have a significant effect of the
mechanical, adhesion, electrophysical, thermophysical and other properties of coatings and
are a criterion, which determines their durability. In this connection, of special importance
are studies of the effect of various physicochemical and technological factors on the value
of stress in the formation and ageing of polymer, in particular, epoxy, coatings.
The value of internal stresses is significantly affected by the molecular mass of molecules of a film former; it has an effect on their flexibility, conformation and structuremechanical properties of the system, as well as the number and nature of bonds, the character of their distribution in the system.
One of the features of polymer coatings is that their structure and properties are inhomogeneous along the thickness of the film and depend on it. The cause of this phenomenon
is due to the uneven hardening of coatings along the thickness of the film and to the effect
of adsorption interaction of the film former with the support. The work presents the data on
the study of the supramolecular structure of various layers of epoxy coatings 50, 200 and
400 m in thickness. The greatest differences in the structure along the thickness of the film
are found for coatings of 50 and 200 m in thickness. As the thickness of epoxy coatings
increases up to 400 m, the inhomogeneity of the structure along the thickness of the coating is preserved, but the size of the structural elements in middle layers ana those bordering
with the air decreases from 300 to 3040 nm, as the result of which the structure becomes
more homogeneous along the thickness of the coatings than for coatings of smaller thickness. A decrease of the size of structural elements, apparently, leads to an increase of the
intermolecular interaction. This is accompanied with an increment of internal stresses with
the increase of the film thickness and decrease of the thermophysical parameters.
Rheological, thermophysical, physicomechanical and structural studies have shown
that at the first stage of coatings formation from oligomer systems local bonds are formed
within the limits of a small number of molecules or between individual associates. The process is accompanied by the formation of supramolecular structures or aggregation of the
available structural elements. At the second stage, links emerge between these structures,
which lead to a sharp inhibition of relaxation processes and increment of internal stresses.
This character of structure formation was observed in the development of the threedimensional network from epoxides and solutions of epoxides.
In production of coatings from solutions of polymers and oligomer systems, to prevent
the formation of an inhomogeneous structure consisting of large aggregated structural elements, at the initial stage of their formation film formers were modified by texturing agents.
These agents contain functional groups capable of chemically interacting with molecules
of the film former and with the surface of solid bodies used as supports and fillers.
-Aminopropyltriethoxysilane (AGM-9) was used as a structural additive to improve
the properties of epoxy coatings. Introduction of a texturing agent in an optimal amount
(0.070.25%) to epoxides was shown to contribute to the decrease of internal stresses in
the system at a simultaneous increase of strength, adhesion and durability of the coatings.
At a large concentration of a modifier (more than 1%), other properties were noted to worsen together with the decrease of internal stresses.

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219

One of the ways to decrease internal stresses in the formation of coatings is the action
of a magnetic field on the system. Under optimal conditions, the magnetic field plays the
role of a dispersant preventing the aggregation of structural elements and contributing to
the formation of a homogeneous three-dimensional network from associated macromolecules. The effect of a magnetic field on structure formation in solutions of epoxy oligomer,
the formation of coatings and their physicomechanical properties have been studied. A
homogeneous globular structure with globules 1520 nm in size was found to be formed
at the action of a magnetic field with the optimal parameters. It was concluded that the action of a magnetic field under these conditions is related not to the orientation of structural
elements along the direction of the force lines, but to the fixation of associates in the oligomer system and to the elimination of the effect of their aggregation in the process of hardening. This character of structure formation contributes to the sharp decrease of internal
stresses, a significant (1.53-fold) increase of adhesion and strength of coatings.
The effect of structuring of the system under the action of a magnetic field, which prevents the aggregation of structural elements in the process of their hardening and contributes to the significant improvement of the physicomechanical characteristics is observed
both for unfilled systems and for systems filled with ferromagnetics and diamagnetics.

6.7

Technology of producing protective polymer coatings

The process of producing polymer coatings consists of main and auxiliary operations. The
former include processes determining the quality of coatings produced: preparation of the
surface of an article prior to the application of material, application of material, hardening
(drying) of material. The auxiliary operations include additional processes improving the
decorative properties of some coatings. For instance, grinding of intermediate layers and
polishing of the upper layers of coatings formed.
Preparation of the surface of an article largely determines the service life of the coatings. Lacquer-and-paint material of even the best quality would not provide for the protection of metal from corrosion, if it is applied to an unprepared surface.
Preparation of the surface of an article for painting is the first operation in the process
of producing coatings.
Performance properties of coatings largely depend on the method of preparation and
the purity of treatment of the surface. The more aggressive the medium in which the article
used is, the more thoroughly its surface should be prepared for painting.
Durability and other performance properties of coatings from the same lacquerand-paint material depend on the process of its production, which is due to the corrosion
resistance of metal, composition of corrosion products formed on the metal surface, technology of fabricating the articles (its shape, configuration, size) and preparation of the surface before painting.
Lacquer-and-paint coatings protect the surfaces of black metals (articles from rolled
steel, iron and steel castings) and nonferrous metals (items from galvanized and cadmiumplated steel; magnesium, aluminium, copper and their alloys).
Preparation of the surface consists in the removal of metal corrosion products (rust),
oxide scale, contamination by fats and conservation agents, by other accretions preventing
a good adhesion of metal to material applied.
The preparation method is chosen depending on the metal from which the item is fabricated, its size and design, the initial state of the surface, the requirements to the class of
coatings and performance conditions of the item.

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

In industry, for items from black metals, use is made of mechanical, thermal and chemical methods of surface preparation. For surfaces from nonferrous metals, treatment with
thermal and partially mechanical methods is totally ruled out. Chemical methods of surface
purification of metal items include degreasing, etching, removal of old coatings, as well as
methods of rust removal and phosphatizing.
An important operation in the coating production process is application of material.
Only the use of advanced, automated methods of application makes it possible to completely realize all the potential possibilities inherent in material itself, and also to prevent the loss
of material, which is especially important in the current deficit of lacquer-and-paint materials.
Progress in the chemistry of high-molecular-mass compounds contributed to the commercial production of various oligomers and polymers and led to the development of
high-quality lacquer-and-paint materials and polymer coatings on their basis. The improvement of the quality of materials and expansion of their range was accompanied with the improvement of the existing and development of new application methods. From manual
methods, such as using brushes, swaps, the industry moved to modern methods: pneumatic,
electrostatic and airless spraying, jet glazing, electrodeposition.
Application of fluid lacquer-and-paint materials on a solid surface is based on:
(a) their conversion to aerosols followed by deposition and coagulation in a thin layer;
(b) wetting of the surface (adsorption);
(c) deposition (sedimentation) of a substance from the liquid medium (solution or dispersion) at the action of an electric current, heating;
(d) adsorption from the gaseous or vapour phase.
The most frequently used method of applying lacquer-and-paint materials is spraying.
Depending on the type of dispersant, there are the following dispersion methods:
pneumatic or aerodynamic spraying without or with heating; in this case, material is
atomized by a jet of compressed air;
hydraulic or hydrodynamic spraying at low and high pressure, with or without heating; in this method, material is supplied under a high pressure via the nozzle of a sprayer as
the result of a sharp pressure differential;
electrostatic spraying, which leads to the formation of aerosol due to the action of
electrical forces.
The second group of methods are dipping, glazing; painting by rolls, in drums, by
brushes and other manual implements. Their performance requires a direct contact of the
solid surface with the liquid lacquer-and-paint material and as complete as possible interaction (wetting).
The recent years witness a noticeably increased interest in the roller method due to the
sharply expanded production of painted sheets and rolls. The roller method compares
favourably with other methods by its high performance, a high coefficient of utilization of
lacquer-and-paint materials, a relatively good quality of coatings (even thickness, absence
of chagrin). Application of materials by this method is an automated process performed on
special roller-type machines.
The electrodeposition method is used to apply water-base lacquer-and-paint materials:
water-borne and water-soluble.
One of the stages of the production of coatings, which determines their quality, is the
hardening of the applied lacquer-and-paint material, which in practice is called drying.
Drying is the process of converting a liquid material into a solid state to form a film.
The state of a lacquer-and-paint coating depending on the duration and temperature of

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221

the drying is characterized by the extent of dryout. By the mechanism of coatings hardening, film formers are divided into two classes. The first class includes film formers, the formation of films from which occurs without chemical reactions due to the physical
dryout determined by the evaporation of the liquid phase. One of the main conditions of
producing coatings based on film formers of the first class is the slow increment of the viscosity of the system. At a rapid evaporation of the solvent, not only surface defects of the
film can be possible in the formed coatings but also large internal stresses, which lead to a
significant decrease of the physicomechanical characteristics of coatings. Besides, in rapid
evaporation of the solvent the different viscosities of the surface and internal layers contribute to the formation of unstable supramolecular structures in the film, which stipulate a
decrease of the physicomechanical and protective properties of coatings. Lacquer-and-paint
materials hardened by the mechanism of physical drying include coatings based on solutions and dispersions of polymers of various chemical composition, cellulose ethers and esters, and other film formers.
The second class of materials hardened by chemical drying includes film formers,
the formation of coatings from which occurs due to the chemical interaction of the systems
components. The hardening process of such coatings is a rather complex phenomenon, as
along with the removal of solvent, it involves chemical reactions contributing to the formation of a spatially crosslinked polymer. This class includes materials based on reactive oligomer, oil-containing film formers and other materials coatings from which in most cases
represent spatially crosslinked polymers.
When choosing the kind, method and regime of coatings hardening, the factors to be
mainly considered are the type of lacquer-and-paint material, type of support, size and configuration of articles, performance and energy intensity.
There are two types of coatings hardening: natural and artificial. In natural hardening,
coatings are dried in the open or indoors at an ambient temperature of 1225C and relative
humidity of no more than 65%. Advantages of natural hardening are the possibility to form
a coating on large-sized articles, simplicity of equipment and low power consumption; however, natural drying is, as a rule, long-term and can not be used commercially for
alkyd-melamine, epoxy, phenol-formaldehyde and other film formers; it also totally rules
out the possibility of automation of the process.
Artificial hardening of coatings is the impact of heat, light, radiation on the material;
they provide for the conversion of liquid material to the solid state prior to the formation of
the film. Depending on the method of impact, the following methods of coatings hardening
are to be distinguished: thermal, ultraviolet light, radiation. Production of aluminium canning strip includes the following process operations: casting of ingots in an electromagnetic
crystallizer, machining of the ingots, heating of the ingots, hot rolling to produce rolled
products, cutting of the side edge, cold rolling, stretch flattening, anodizing and lacquering,
longitudinal cutting of the strip or transverse cutting for sheets, packaging of the final material. The quality of the surface of aluminium plays the main role in its use for fabrication
of canning containers. If the surface of aluminium does not correspond to the imposed requirements, all advantages of its use lose importance. Therefore, cold-rolled metal is subjected to a special surface treatment, as the result of which the natural oxide film is
substituted for the artificially created one, with a certain structure and properties. This is
achieved by the method of anodic treatment.
Formation of the anodic film is the result of two simultaneous processes: electrochemical formation of the film and its chemical dissolution. At the initial stage, when current
passes through the electrolyte in which aluminium serves as an anode, negatively charged

222

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

oxygen ions move to the anode, where they discharge by coupling with aluminium. As the
result of this reaction, a thin continuous film of aluminium oxide is formed on the surface.
Under the dissolving action of the electrolyte, this continuous film is converted to a porous
film. Oxygen ions penetrate through the porous film, and a continuous film again is formed
under it. Thus, in the anodizing process the porous film gradually becomes thicker to form
a cellular structure.
The thin film under the pores is also called the barrier layer and is a protection from
corrosion. To increase its protective functions, the pores are to be occluded. The pore occlusion process is called consolidation and is achieved by a special treatment or application
of a lacquer-and-paint coating.
Anodizing of the aluminium canning strip is performed on a complex continuous line,
where the anodizing and lacquering processes are carried out consecutively.
Depending on the purpose of canning aluminium, one or both sides of the strip are lacquered. In the two-side process, the lacquer is applied simultaneously on both sides of the
continuously moving strip by means of rubber rollers. The thickness of the lacquer film is
regulated from 2.5 up to 6 m. The thin coating is applied on the side, which will be outer
after the cans are fabricated. The thickness of the applied layer is determined by many parameters: the gaps between the rollers, the ratio of the peripheral speeds of rotation of the
rollers and the transport of the covered surface, the distribution of the lacquer-and-paint material between the surfaces after the gaps are passed.
Drying of the lacquer is performed in a convection-type tunnel drying furnace. As lacquer is applied simultaneously on both sides, when passing through the furnace the strip is
not supported but is held due to the tension. The maximally admissible sag of the strip and
the strength of metal determine the length of the drying furnace, and, therefore, at a fixed
velocity of the strip transport equal to 60 m/min, the drying time, which is 3040 sec. Special lacquers prepared based on epoxy, phenol and vinyl resins and capable of being dried
at a temperature of 250350C, are used for coatings of canning containers. When choosing
the type of lacquer, one should take into account the performance conditions of the coatings.

6.8

Specific features of forming epoxyphenol coatings for canning


containers

Introduction of aluminium alloys in canning industry instead of tinplate opens wide possibilities for manufacturers of cans. Such, for instance, as fabrication of cans of various configurations by stamping, decrease of their weight, increase of the productivity of stamping
automatic machines, due to the fabrication of cans directly from rolls, development of new
types of closure, in particular easily opened lids. However, aluminium alloys, in contrast
with, for instance, hot-dipped tinplate, could not be used in canning industry without a protective lacquer-and-paint coating.
Compositions used the most for protection of canned food containers are epoxyphenol
lacquers. A combination of epoxy oligomer and phenol-formaldehyde oligomer in these
lacquers enables production of coatings with high adhesion to the support and good physicomechanical properties, inherent in epoxy materials, and high protective properties characteristic of phenol-formaldehyde lacquers.
Until recently, epoxyphenol compositions were made up mainly empirically, because
the processes occurring in the interaction of epoxy and phenol-formaldehyde oligomers
were studied insufficiently. Up to the present, the scientific bases of creating compositions
from epoxyphenol systems and protective coatings resistant to biochemically active media

CHAPTER 6

223

b.10, MPa

2
3
1

10

4 , min

Figure 6.1 Effect of the ratio of the epoxy and phenol components on internal stresses: 1,
EO/OAPFO = 75:25; 2, EO/OAPFO = 70:30; 3, EO/OAPFO = 80:20.

have not been developed. In this connection, epoxy and epoxyphenol lacquers for chemically stable protective coatings produced in this country are characterized by a low stability
to biochemical media, in particular, to solutions of organic acids (acetic, lactic, malic), to
enzymes, amino acids and other components of food media. Interaction of epoxy and phenol oligomers has been shown to be of a complex character due to the presence in them of
various functional groups, which can react one with another. Herewith, the probability of
some or other reactions, and, therefore, the properties of coatings depend both on the initial
composition and on the conditions of coatings formation: the presence of catalysts, plasticizing additives, application and drying of lacquer compositions, type of solvent, character
of the support (Fig. 6.1).
Most often, epoxy lacquers are produced based on high-molecular-mass epoxy dianic
oligomer. It has been shown that the optimal set of coatings properties is provided for by
~ 3500. Herewith, it has been
the use of epoxy oligomers (EO) with the molecular mass Mn
found that the elasticity of coatings increases with the rise of molecular mass of EO, but
their chemical endurance to acidic media decreases.
Coatings based on low- and medium-molecular-mass (molecular mass up to 2000) EO

proved to be non-acid-resistant. Only introduction of high-molecular-mass oligomer (Mn


~ 3500), but in the amount of no more than 40%, provided for a sufficient acid resistance
of the coatings. It has also been shown that introduction of high-molecular-mass EO into
epoxyphenol compositions based on low-molecular-mass EO leads to an increase of the adhesion strength of the coatings.
As a rule, PFO of resol type are used to produce can varnishes. Minor amounts of
cresols, xylenols, naphthols are used as the phenol component. Introduction of PFO on substituted phenols, for instance, p-tert-butyl phenol, to epoxyphenol compositions contributes
to the increase of the physicomechanical properties of coatings. However, chemical endurance and the depth of hardening of the coatings increase at the increase of the content of
unsubstituted phenol in PFO. With the increase of the share of EO in the system, the elasticity of the coatings was found to rise; and as the share of PFO increased, chemical endurance increased, which is of special importance in production of canning strip.

224

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

5
1

b.10, MPa

2
3
1
4
0

10

10

20

30

, min

Figure 6.2 Kinetics of the change of internal stresses in hardening of epoxyphenol compositions: 1,
EP-5118 without fc; 2, EP-5118 with fc; 3, EPC based on OAPFO with fc; 4, EPC based on OAPFO
without fc.

In most cases, to produce lacquers, initial EO and PFO are mixed at a given ratio and
are subjected to a preliminary heating forcondensation. The purpose of forcondensation
is to improve the compatibility of EO and PFO, which are poorly compatible at the usual
temperature. It has been noted that a preheating improves the properties of coatings of even
well compatible oligomers, decreases internal stresses (Fig. 6.2). A relationship between
the processes of structure formation in solutions and the structure and properties of coatings
has been established. It has been shown that the structural features and performance properties of coatings based on epoxyphenol compositions are determined to a significant extent
by structural transformations, occurring at the stage of matching EO and PFO solutions
their forcondensation.
In diluted solutions (in ethyl cellosolve) of EO and PFO and compositions on their basis, the primary structural formations are associates of molecules. The affinity to association
is sufficiently pronounced in such solutions owing to the high molecular mass and polarity
of the initial components.
As the molecular mass of EO rises, the extent of structuring of solutions considerably
increases. The structures emerging in concentrated solutions of epoxyphenol compositions
have the character of a fluctuation network from associates of macromolecules.
Forcondensation leads to the change in the character of interaction in solutions of epoxyphenol compositions, which is due to the accompanying chemical and physicomechanical processes. It has been found that in forcondensation owing to intensive thermal motion
of macromolecules and mechanical impact on the solution, there occurs the dispersion of
macromolecule associates, which is accompanied with a decrease of the viscosity of the solution. Disruption of the structure in the process of heatup also leads to the change of the
composition of associates.
An increase of the structural inhomogeneity of forcondensates heated under optimal
conditions leads to an increase of the uniformity of the distribution of the structural

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225

6
1
3
2

in, MPa

5
4
3
2
1
0

1.0
3.0
2.0
Forcondensation time, h

4.0

Figure 6.3 Dependence of the ultimate values of internal stresses in coatings from epoxyphenol
forcondensates heated at 100C (1), 120C (2) and 130C (3), on the duration of forcondensation.

elements in hardened coatings, which, in turn, contributes to the decrease of internal stresses
and an improvement of performance characteristics of coatings. Evidently, the formation
of a homogeneous small-globular structure, where the formation of chemical and physical
bonds is maximally realized, provides for the rigidity and stability of the spatial structure
of a highly crosslinked polymer. This, in turn, determines the high strength and protection
properties of coatings.
The further heating leads to the aggregation of structural elements to larger associates,
as the result of which a defect network is formed. Internal stresses in such coatings are twice
as large as in coatings with the homogeneous small-globular structure, which can be due to
the emergence of large structural elements, at the interface of which an internal stress is concentrated (Fig. 6.3).
Thus, the properties of coatings can be regulated by changing the size of the structural
elements in solutions of forcondensates. Optimal from the point of view of achieving the
homogeneity of solutions, and, therefore, hardened coatings, is the heating at 120C for
1.52.0 h depending on the molecular mass of the EO used; its increase leads to the increase
of the optimal time of forcondensation (Fig. 6.4).
The choice of the forcondensate hardening regime is of great significance. It is known
that the correct choice of the temperaturetime conditions of forming coatings would make
it possible to produce coatings with an optimal supramolecular structure, which provides
for their high performance properties. In this connection, the authors studied the effect of
the hardening regime of epoxyphenol coatings on their structural features and physicomechanical characteristics. It was found that the process of forming coatings was considerably
accelerated with the rise of temperature and at the hardening at higher than 300C occurred
within several seconds (3040 sec). The completeness of the coatings hardening was controlled by the content of the gel fraction. The most complete hardening of the system is
achieved at 280300C (the content of the gel fraction, 7580%). Within the temperature
range above 300C, thermooxidative destruction of polymer begins; it is accompanied with
an intensive loss of the mass, and with the increase of the content of EO in the composition
the thermodestruction onset temperature slightly decreased.

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

5
4
1

4
in, MPa

2
3

2
1

3.0
4.0
2.0
Hardening time, h

1.0

5.0

6.0

Figure 6.4 Change of internal stresses in the formation of coatings from epoxyphenol compositions
heated at 100C (1), 110C (2), 120C (3) and 130C (4), Thard = 200C.

1
2
4

in, MPa

4
3

2
1

1.0

2.0

3.0
5.0
4.0
Hardening time, h

6.0

Figure 6.5 Change of internal stresses in the hardening at 200C of coatings produced from: 1, A
mechanical mixture of epoxy and phenol-formaldehyde oligomers (E-04Kr:FKoF-4 = 80:20 wt. %);
2 4, forcondensates heated for 0.5 h (2), 1.0 1.5 h (3) and 3 6 h (4); 5, forcondensation without catalyst, hardened with H3PO4.

We also showed how the change of the temperature regime of formation affects the
structural features of coatings. It was concluded that the high-temperature hardening of epoxyphenol coatings (at 350390C) is undesirable, as intensive destruction processes lead
to a worsening of the performance properties of coatings. The conclusion was made that the
optimal formation temperature of epoxyphenol coatings is 250300C (Fig. 6.5).
As we already said, coatings are formed based on a preliminarily obtained forcondensate by heating a mixture of alcohol solutions of oligomers at 100120C for several hours.
Due to the diversity of combinations of functional groups in epoxyphenol compositions, the chemical reactions occurring in forcondensation and hardening are rather diverse.
Herewith, the probability of this or that reaction depends both on the composition and

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227

conditions of these processes their temperature, duration, presence and type of catalyst.
Studies carried out at the Chair of the Chemistry and Technology of Lacquers, Paints
and Coating Compositions, D.I. Mendeleyev University of Chemical Technology,
Moscow, made it possible to establish the main schemes and kinetic regularities of the reactions proceeding in forcondensation and hardening of such compositions.
It has been shown that under conditions of acid catalysis in forcondensation there is
no chemical interaction between epoxy and phenol-formaldehyde oligomers. Epoxy oligomer reacts to the catalyst orthophosphoric acid by the scheme
OH
CH

CH2 + HO

OH
O

CH

CH2O

OH

OH

(I)

OH

OH
CH

CH2 +
O

CH

CH2

OH

OH

OH
CH

CH2O

O
O

CH

CH2O

OH

O CH2

CH

OH

(II)

OH

O
CH

CH2 + HO
O

(O

CH2

OH

CH)2
OH

(CH

CH2O)3

(III)

OH

Herewith, all three hydroxyl groups prove to be reactive with respect to the a-oxide
groups of epoxy oligomer.
Phosphate groupings formed by reaction (I)(III) in the presence of orthophosphoric
acid and partial organic phosphates are readily subjected to hydrolysis, owing to which
a-oxide groups of epoxy oligomer turn to glycol ones.
The presence of orthophosphoric acid and partial phosphates also contributes to the
interaction (proceeding at a sufficiently high rate) of a-oxide groups of epoxy oligomer with
the dissolving alcohol (ethyl cellosolve or n-butyl alcohol introduced into the reaction mixture together with phenol-formaldehyde oligomer):
CH

CH2 + HOR

CH(OH)CH2OR,

(IV)

where R is C2H5OCH2CH2 or HC4H9 .


Phenol-formaldehyde oligomer in the presence of orthophosphoric acid is subjected
to etherification by the same alcohols.
OH

OH

(V)

+ HOR
CH2OH

CH2OR

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Forcondensation under conditions of the basic (in particular KOH) catalysis, efficient
for the reaction of a-oxides with alcohols, leads to the formation of epoxyphenolformaldehyde copolymers. In this case, there also occurs condensation of methylol groups
of resol oligomer

HO

CH2

(VI)

OH + CH2O + H2O

CH2OH

and their etherification, predominantly by ethyl cellosolve


OH

OH

(VII)

+ HOCH2CH2OC2H5
CH2OH

CH2OCH2CH2OC2H5

The features of hardening of the epoxyphenol composition are determined by the nature and ratio of the functional groups remaining after forcondensation, as well as the hardening conditions (temperature, type and concentration of the catalyst used). In industry,
epoxyphenol coatings are usually hardened at high temperatures. Thus, for instance, can
varnishes on tinplate are hardened at temperatures of 473523 K (200250%) for 10 min;
and on aluminium, at 633 K (360C) and higher for 3040 sec.
As a hardening catalyst of epoxyphenol compositions, orthophosphoric acid is used
the most often.
The study of the hardening process (T = 473 K) has shown that in this case a-oxide
groups of epoxy oligomer react with phenol hydroxyl groups:

CH

CH2 + HO

CH

CH2

(VIII)

OH

and with secondary hydroxyl groups:


CH2
CH

CH2 + CH2
O

CH

CH2

CH

CH2

CH

(IX)

CH2

OH

Besides, secondary hydroxyl groups enter into a re-etherification reaction with phosphate groupings formed in the reaction of orthophosphoric acid with epoxy oligomer at the
stage of forcondensation. However, the greatest rate in the hardening is with the reactions
of methylol groups of resol between one another and with etherified methylol groups:

2 HO

CH2OH

HO

CH2OCH2

OH

(X)

CHAPTER 6

HO

CH2OH + ROCH2

HO

CH2OCH2

229

OH

(XI)

OH

All reactions with participation of methylol groups are catalyzed by orthophosphoric


acid and its partial esters.
Besides, it has been found that under conditions of high (473 K) temperatures the hardening can not occur due to the interaction of secondary hydroxyl groups with methylol ones,
because the groupings formed in this reaction are unstable at temperatures higher than
175C and are subjected to further conversions as follows:
CH2

CH

CH2

CH2

CH

OH
+
CH2OH

OH

OH

CH2

CH2

CH2

(XII)

Products of further
conversions
(oxidation, polymerization)

As a catalyst of hardening of epoxyphenol compositions, the most frequently used


agent is orthophosphoric acid, whose introduction accelerates the hardening process. This
is supported by experimental data. Thus, introduction of an additional amount of catalyst
orthophosphoric acid increases the content of the gel fraction in the hardened film. However, the amount of orthophosphoric acid added should be minimal as far as possible, because in this case lacquers are distinguished by a better stability, and their hardening
(especially under high-temperature conditions, at 360C) would be complicated to a smaller
degree by undesirable oxidative side reactions of phenol-formaldehyde oligomer, which deteriorate the quality of coatings.
It is noted that the considerable change of the properties of epoxyphenol coatings can
be achieved by introduction of minor amounts (35%) of oligomer modifiers into initial
compositions. Introduction of such additives makes it possible to create an ordered structure
in epoxyphenol systems and coatings on their basis and to improve significantly their properties. The structural transformations occurring in epoxyphenol compositions depend on the
type and functionality of the modifying oligomer, as well as on the ratio of viscosities of
oligomers and their matching conditions.

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7
7.1

Ways of Increasing
the Protective Properties
of Coatings for Canning
Containers

Coatings with enhanced adhesion to aluminium and its alloys

It is much more difficult to obtain a coating with a high adhesion to aluminium and its alloys
than to most other metals, because at other equal conditions adhesion of polymers decreases
in the sequence: nickel, steel, iron, copper, brass, aluminium, tin, lead.
Special attention is paid to the possibility of producing coatings, which satisfy the
stringent requirements for adhesion, water resistance and capability of hardening under
conditions of comparatively low temperatures up to 120C. One of the major ways to increase adhesion and water resistance of coatings based on epoxy compositions is modification of oligomers or introduction of various additives, improving adhesion and water
resistance, into compositions. To improve the adhesion properties, it is proposed to introduce up to 20% modifying polymers, which possess a lower surface tension as compared
with the main polymer, as well as various organosilicon compounds in the amount from
0.01 up to 20%. Among other substances, modifying polymers include (CH2)3Si(OCH3)3,
Br2C6H3Si(OCH3)3, (CH3)2N(CH2)3Si(OCH3)3.
It has been shown that minor amounts of polymethyl silazan significantly improve adhesion, water resistance and other performance parameters. As active thinners, it is recommended to add glycidoxysilanes. The effect of increasing adhesion to metals, especially to
aluminium and its alloys, as well as an improvement of water resistance is revealed in modification of epoxy compositions by epoxysilane in the amount of 0.15%; this modification
increases the strength of coatings.
Silicon-containing compounds are used as modifiers of epoxy oligomers; herewith,
mixture compositions are used. Good results are observed in introduction of 3070% of
epoxy oligomer modified by siloxane compounds.
An increase of adhesion to aluminium and resistance of coatings to the action of boiling water and 5% alkali liquor is observed in modification of epoxy coatings by epoxyurethane oligomers or polyurethanes with terminal isocyanate groups, which are produced by
the interaction of various diisocyanates with diols having molecular masses up to 200, at a
ratio of diisocyanate to diol from 1.2:1 up to 1.75:1. These compositions are recommended
as primers with increased adhesion to aluminium. For this purpose, epoxyurethane oligomers, containing aliphatic epoxy oligomer were developed.

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Polymers, which are products of combined modification of epoxy oligomers with acrylates and diisocyanates, were found to have similar properties. These compounds contain a
set of active groups, such as carboxyl, hydroxyl, epoxy, methylol, amide and amine ones.
Polyisocyanates are capable of hardening at room temperature to form coatings with
high mechanical properties and adhesion to metals, as epoxyurethanes with a three-dimensional structure are formed in the process of their hardening. From the comparison of potentially possible ways of introducing urethane groups into epoxy oligomer as the result of
their modification and hardening of epoxy compositions by polyisocyanates, the former
should be recognized to be the best approach, because it is not associated with the use of
toxic isocyanates in preparation of lacquer compositions. In this case, the application process is harmless and yields compositions stable in storage and air moisture-resistant. A
promising way is to use as hardeners compounds with urethane groups, containing no free
isocyanate groups. In this case, the reaction of hardening is provided for by the presence of
other functional groups capable of reacting with epoxy oligomer in the hardener. Coatings
of this composition are hardened at room temperature for seven days and are distinguished
by good adhesion and mechanical properties and low water absorption. Similar parameters
are characteristic of coatings from epoxy oligomers with hardener Versamide A-115.
Epoxy coatings hardened by compounds in which the silicon atom is bound to amino
or aminosubstituted groups, as well as compounds of the type of alkoxysilyl propylamine
have been shown to have high performance properties. These compositions are used for protection of metal surfaces in contact with hot water. Their structure is
R1
H2N

R2O

Si

R2

NH2,

R2

where R1 (CH3)n , C2H5

, C3H7 , C6H5, R 2

(CH2)x

, x = 2 4; n = 1 30.

An increase of adhesion of coatings to aluminium was achieved by a special treatment


of metal before lacquering. For this purpose, use is made of primers based on products of
the interaction of oxyalkyl(meth)acrylates with anhydrides of dicarboxylic acids. They are
best to be applied to the metal surface before lacquering.
The formulation of similar compositions often includes silicon-containing compounds, such as epoxysilanes and aminosilanes. These additives make it possible to increase two times the adhesion of coatings to aluminium. Application of these compounds
improves the properties in painting metals with compositions based on other polymers.

7.2

The role of solvent in the formation of the properties of coatings for


canning containers

Polymer compositions based on epoxy oligomers are widely used in production of protective and decorative coatings on canning containers. Along with a rich set of properties (high
adhesion and cohesion strength, resistance to alkali liquors), they possess an insufficient
chemical endurance to organic acids (acetic, lactic, tartaric etc.), stamping, as well as instability of the performance properties. It has been shown that the instability is due to the emergence of internal stresses owing to the slowdown of the relaxation processes in the
formation and operation of coatings. A significant effect on the value of internal stresses
and the kinetics of their increment is rendered by the specific features of the structure

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233

formation in oligomer systems. This is stipulated by the fact that dilute and concentrated
solutions of oligomers are strongly associated systems.
It has been found that the structure of associates, their size and morphology depend on
the chemical composition of oligomer, the nature of solvent, the conditions of coatings formation and other physicochemical factors. In particular, a significant effect on structural
transformations in epoxy compositions, as well as on the structure and properties of coatings, is rendered by the nature of solvent.
The effect of the nature of solvent on structure formation in epoxy and epoxyalkyd
compositions, as well on the structure and properties of coatings on their basis, used for canning containers to improve their performance properties, was studied.
Compositions were produced on the basis of epoxy oligomer E-33 and its mixture with
alkyd oligomer at a ratio of 70:30. Orthophosphoric acid was used as a catalyst of hardening. Coatings were applied using 50% solutions in solvents widely used in industry and distinguished with the affinity to oligomer systems: xylol, tributyl phosphate, ethyl cellosolve,
carbitol, butyl glycol.
The rheological properties were studied on a Shvedov-type instrument with coaxial
cylinders. The structure of coatings was studied by the method of electron microscopy by
taking carbon-platinum replicas from the surface of coatings subjected to oxygen etching
in the optimal mode. The adhesion strength of coatings to aluminium was determined by
the detachment method. The stressstrain parameters were studied on an Instron instrument.
The gloss of coatings was assessed on a goniophotometer. The coating-formation process was studied by comparing the kinetics of increment of internal stresses with that of polymerization and release of the solvent at various stages of hardening. The quality of the
solvent was assessed by the rheological properties of the solutions of oligomers.
From the data on the dependence of viscosity on shearing stress for solutions of epoxy
oligomer in various solvents and in mixtures of tributyl phosphate with butyl carbitol (BC)
and butyl glycol (BG) at a ratio of 1:2, it follows that all solvents are in practice semistructured systems or Newton-type compositions. The lowest viscosity was observed for solutions of oligomer in butylene glycol. Solutions of oligomer in tributyl phosphate (TBP) and
carbitol (C) are distinguished with a much higher viscosity. Herewith, the initial solvents
are semistructured systems, which differ little one from another by the character of the rheological curves.
In accordance with the HildebrandScatchard theory, the quality of a solvent with respect to a polymer can be assessed by the similarity of the values of their solubility parameters; it is the square root of the cohesion energy density. When assessing the affinity of a
solvent to a polymer, it is also desirable to take into account the contribution to the cohesion
energy density of intermolecular forces of diverse nature (dispersion, polar, hydrogen, association interaction). The interaction of each of these types is taken account of by determining, respectively, parameters d, p, h, a).
The characteristics of epoxy compositions studied and solvents used are presented in
Table 7.1.
By the proximity of the parameters of solvents solubility and epoxy composition, all
systems can be arranged in the sequence: butylene glycol, ethyl cellosolve, carbitol, tributyl
phosphate, xylol.
Butylene glycol and ethyl cellosolve, along with dispersion interaction, also exhibit
other types of intermolecular interaction characteristic of a film former. This is indicative
of a better quality of these solvents as compared with others.

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Table 7.1 Solubility characteristics of epoxy oligomer and solvents.


Compounds

Epoxy composition
Butylene glycol
Ethyl cellosolve
Carbitol
Tributyl phosphate
Xylol

Solubility parameters (MJ/m3)1/2

Thard, C

230
130
202
177
138

23.5
23.0
24.1
22.4
18.6
17.8

17.3
15.9
16.0
15.4

11.2
5.7
9.3

11.2
15.7
14.3

15.9
16.7
17.4
16.3

17.2

The quality of a solvent was also assessed by the rheological properties of the solutions
of oligomers. From the data on the dependence of viscosity on shearing stress for solutions
of oligomers in various solvents and in mixtures of tributyl phosphate with carbitol and
butylene glycol at a 1:2 ratio, it follows that all solutions represent semistructured or
Newton-type systems. It could be suggested that solutions of oligomer in a good solvent
would form coatings with the finest and homogeneous structure and, respectively, with a
greater density of the three-dimensional network and better physicomechanical characteristics. However, the obtained experimental data on the effect of the nature of solvent on the
network density, structure and properties of coatings failed to confirm this suggestion. By
the method of electron microscopy, it has been found that coatings from solutions of oligomer in tributyl phosphate are distinguished by the most homogeneous structure with the size
of morphologically anisodiametric structural elements of 1015 nm. With the quality of the
solvent improved, structural elements are observed to aggregate to form a nonhomogeneous
globular structure. The size of aggregates increases in passing from carbitol to butylene glycol and xylol up to 0.20.5 m.
To elucidate the causes of this phenomenon, the process of coatings formation from
solutions of oligomer in various solvents was studied by comparing the data on the kinetics
of the release of solvent and the kinetics of polymerization of compositions with the change
of internal stresses in the process of hardening. From the kinetics of increment of internal
stresses in the formation of coatings at 180C from solutions of oligomer in various solvents, it follows that the least internal stresses are observed in the formation of coatings
from solutions of oligomer in tributyl phosphate, as well as in its mixture with other solvents. With the quality of the solvent improving or worsening, internal stresses increase;
what is more, spontaneous delamination of coatings is observed for coatings from solutions
in xylol. From the data on the kinetics of the release of the solvent in the formation of epoxy
coatings under the same conditions from solutions of oligomer in various solvents, it follows that the solvent is eliminated the most rapidly in the formation of coatings from solutions of oligomer in butylene glycol. With the quality of the solvent worsening, the time up
to its equilibrium concentration in the system increases and the rate of its evaporation sharply slows down. This indicates that the chosen solvents interact with oligomer differently,
though its boiling temperature is the same as the boiling temperature of butylene glycol.
When studying the effect of the nature of the solvent on the polymerization kinetics of
compositions, a significant part of chemical bonds has been found to emerge after the solvent is released. This indicates the occurrence of polymerization in the solid phase, i.e., after
the solvent release. With the release rate increasing, the incompleteness of the relaxation
processes also rises, which is accompanied by a sharp increment of internal stresses.

CHAPTER 7

235

Similar regularities were obtained in studies of structure formation in solutions of


epoxyalkyd compositions filled with rutile dioxide. From the data on the dependence of viscosity on shearing stress for solutions of an epoxyalkyd composition in various solvents, it
follows that by the absolute value their viscosity is larger than that of epoxy oligomers.
However, the regularities of the effect on the nature of the solvent on the rheological properties of compositions remain the same. Solutions of compositions in a good solvent are distinguished with the lowest viscosity. With the worsening of the quality of a solvent, the
viscosity increases. Similar regularities are also observed in the kinetics of solvent release
in the formation of epoxyalkyd compositions.
From the data on the effect on the nature of solvent on the kinetics of increment of internal stresses in the formation of coatings from epoxyalkyd compositions, it follows that
the lowest internal stresses emerge in coatings from solutions of oligomer in tributyl phosphate and its mixture with other solvents. The disturbance of the law of additivity in the
change of internal stresses in coatings from mixture compositions based on butylene glycol
and tributyl phosphate is due to the worsening of adhesion properties of coatings and their
spontaneous delamination.
Coatings from compositions with an optimal affinity of oligomer to solvent and the
rheological properties are characterized by the highest strength parameters and adhesion
strength, which was used in the development of systems for canning containers (Table 7.2).
Table 7.2 Effect of a solvent on tensile strength (p), adhesion strength (A) and gloss of epoxy
alkyd coatings.
Solvent
TBP
C
TBP:BK (1:2)
BG
TBP:BG (1:2)

A, MPa

p, MPa

Gloss, %

1.0
2.3
3.8
4.0
3.6

29
27
27
15
20

80
60
65
5
30

To improve the quality of epoxyphenol coatings, it is recommended to subject the mixture of solutions of oligomers in ethyl cellosolve to forcondensation, i.e., heating at
373393 K for several hours. Epoxy and phenol-formaldehyde oligomers do not interact
in the course of forcondensation.
The changes occurring in ethyl cellosolve in the process of forcondensation were studied with the view to establish the relation between the optimal duration of forcondensation
and the properties of initial epoxy oligomers and to elucidate the causes of coatings properties worsening at a prolonged forcondensation exceeding the optimal value. No changes
occur in epoxy oligomers heated without solvents, whereas in phenol-formaldehyde oligomers changes are in principle possible due to their large reactivity. As an object of study,
use was made of a mixture of epoxy oligomer E-05k (molecular mass, 20003000) in ethyl
cellosolve. Changes occurring during the heating of this system were studied by calorimetry
and by the method of dielectric characteristics measurements. Changes in ethyl cellosolve
during the heating were determined by the spectroscopy method.
A sharp decrease of heat liberation at the final stage of forcondensation for solutions
of epoxy oligomer in ethyl cellosolve, absent in pure solvent, implies the emergence of an
additional endothermic process superimposed on the exothermic process of regrouping of
the elements of the ethyl cellosolve structure. This phenomenon is explained by that the

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time of disaggregation of associates depends on the initial structure of epoxy oligomer.


Using the fractionation method, a fraction containing mainly large structural elements was
isolated in epoxy oligomer as the lower phase. Between two phases close by their molecular
mass distribution and chemical structure, the solvent was distributed differently. The content of nonvolatiles in the lower phase exceeds the concentration in the upper phase approximately sixfold, whereas for other specimens only 1.6-fold. This indicates that the
associated lower phase is in fact matched with a smaller amount of solvent than the initial
oligomer, which requires a larger heating time to disaggregate the structure. For the other
phases, the affinity to the solvent differs insignificantly. The suggestion on the effect of the
redistribution of the solvent between two phases on forcondensation time is confirmed by
the fact that for lacquers, obtained separately from the lower phase or upper phase, the
optimal time of forcondensation does not exceed 2 h irrespective of the optimal time of
forcondensation for the initial oligomer.
After the endothermic process, calorimetric studies fail to find the existence of any
exoprocess, which could be treated as a disaggregation of associates. It is assumed that the
extreme character of the dependence of the coating quality on forcondensation time can be
explained by an antiplasticizing, association-contributing action of the phenol formaldehyde oligomer.

7.3

Effect of the nature of epoxy oligomers on the properties of coatings

Possessing a high resistance to various aggressive canned media, coatings based on epoxy
resins etherified by fatty acids of various plant oils as well as isocyanates are insufficiently
stable to organic acids (acetic, etc.), so they can not be used for protection of canning containers from corrosion.
Hardening of epoxy resin-based can varnishes by phenol-formaldehyde forcondensators is accompanied with a number of reactions (interaction of methylol and butoxyl groups
of phenol condensate with epoxy and hydroxyl groups of epoxy resin, which affect the quality of the final product). The choice of the optimal ratios of the components and regimes of
hardening of compositions presents significant problems and is in many cases empirical.
To produce acid-resistant coatings, high-molecular-mass epoxy resins are used, with
molecular masses higher than 12,500 and alcohol-soluble resols (phenol resols or cresol
resols), both butanolized and non-butanolized. As phenol resols, Novolac resins and 100%
reactive resins can be used. For better hardening of epoxyphenol compositions, 12% phosphoric acid is added. Epoxy-phenol lacquers dry up at a temperature of 180200C for
2030 min. To increase the quality of epoxyphenol coatings, the mixture of resin solutions
is subjected to forcondensation under optimal conditions.
In Czech Republic, epoxyphenol compositions are used for coating tinplate sheets.
Compositions have been developed, which dry up at 200205C for 15 min. The properties
of coatings based on low-molecular-mass epoxy resins E-40 and E-41, as well as mediumand high-molecular-mass epoxy resins, obtained from fusing low-molecular-mass resins
with diphenylol propane (resins E-44 and E-49) and emulsion condensation of diphenylol
propane with epichlorohydrin (resins E-15 and E-0.5) have been studied.
Modified and non-modified resol resins were used as phenol-formaldehyde resins.
Each epoxy resin as a 50% solution in a solvent matched with one of the phenol resins at
70:30, 60:40, 50:50, 40:60 and 30:70 ratios. The complete match of the resins was assessed
by the transparency of the film after the drying at 150160C of the mixture of resins
applied to glass.

CHAPTER 7

237

It has been found that at room temperature low-molecular-mass epoxy resins match
with phenol resins, as cresol-formaldehyde resin K-212-01 with the softening temperature
of 6266C matches with the content of methylol groups 5.05.5% and with the 100% phenol formaldehyde resin No 101 with the similar softening temperature and with the 80%
content of methylol groups (produced based on n-tert-butyl phenol), as well as with phenol
formaldehyde butanolized by condensate modified by Chinese wood oil (resin No 241).
With these resins, low-molecular-mass epoxy oligomers almost do not match. The complete match of these components is achieved only after their heating at 120125C for 1.5
h. Medium- molecular-mass epoxy resins match at room temperature with all phenolformaldehyde resins at given ratios. High-molecular-mass epoxy oligomers E-49 and E-0.5
match with resins K-212-01 and No 101 at all ratios at room temperatures, and with resin
No 241 only after a heating up to 100125C for 1.52 h. With resin based on xylenol-formaldehyde butanolized KF and the product maximally butanolized with phenol-formaldehyde condensate MBP, high-molecular-mass epoxy resins match both at room
temperature and after heating at 120130C, but not at all ratios. At ratios of these components of 70:30, 60:40 and 30:70, the matching occurs at room temperature, and at ratios of
50:50 and 40:60 they do not match even after heating.
To produce coatings, lacquers were applied by the pouring or dipping method on
hot-dipped or electrolytic tinplate preliminarily degreased by a solvent and calcined at
180C for 1530 min. The thickness of the film was 46 m.
Chemical endurance of coatings was determined by boiling lacquer plates in a 3%
solution of acetic acid, 3% cooking salt, 2% solution of tartaric acid. Additionally, the coatings were held in these solutions in autoclaves at 121C and pressure from 2.5 atm for 1 h.
Those coatings, which had no blisters, delamination or leadiness after boiling in acetic acid
were considered to be chemically stable.
Coatings having an impact strength of no less than 50 kgcm (a U-1 instrument), an
elasticity no less than 6 mm (an E press), a pendulum hardness no less than 0.8 and a bend
no more than 1 mm, were considered to be mechanically strong.
It has been found that all these epoxyphenol compositions form water-resistant coatings. Acid-resistant proved to be only coatings based on compositions with high molecular-mass epoxy oligomer in the amount of no more than 40%.
Coatings based on low- and medium-molecular-mass epoxy oligomers are non-acidresistant. The greatest stability was shown for coatings based on resins E-0.5 in a combination with KF at a ratio of components 40:60, 30:70; resins E-0.5 and K-212-01 at a ratio of
30:70; E-49 and KF at a ratio of 40:60, 30:70. The results of storage of preserves with acid
media for 1 year have shown that coatings based on an epoxyphenol composition possess
much higher protective properties as compared with oil-based materials.

7.4

Water-base compositions for protection of canning containers

The inner and outer surfaces of metal canning containers are protected using ecologically
benign lacquer-and-paint materials: powder, with a high content of nonvolatiles, aqueous,
of radiation hardening.
Special attention is given to canning containers with protective coatings based on
water-base systems. The priority in this field is with the USA, where the demand for aqueous materials in production of canning containers increases annually by more than 19%. In
the years coming this parameter is assumed to reach 100%. The major reasons for the increasing demand of aqueous compositions is a decreased content of organic solvents

238

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

(2025% less as compared with traditional lacquers), lower toxicity and fire hazard, simplicity and accessibility of application methods. The world market offers a wide range of
water-base materials. However, only the systems, which satisfy the specific requirements
to materials in contact with food products, are suitable for protection of canning containers.
The major of them is inertness of coatings with respect to a canned product, the stability in
storage for no less than 12 months, the processibility, a high adhesion of coatings to the metal surface, the stability to the effect of hot water and acids, the stability to sterilization and
pasteurization. Coatings based on water-base systems should be of high quality, and their
performance properties and efficiency should not be worse than those of traditional lacquer
coatings.
Water-base compositions based on epoxy, acryl, epoxyacryl, vinyl etc. film formers
satisfy these requirements to different degrees. The choice of material is determined in each
particular case by the type of metal used, container fabrication method, type of canned product. The most widespread film formers for water-base canning materials are carboxylcontaining epoxy oligomers and epoxyacrylates. Various methods are used for their synthesis. The simplest of them is the interaction of epoxy oligomers with dibasic acids or their
anhydrides. The drawbacks of these methods are the process difficulties related to the
two-stage synthesis, a large duration of the process and a high cost of the product.
Aqueous materials having a high stability and processibility are obtained in the reaction of epoxy oligomer with aromatic amino acids; oligomers formed possess an increased
stability.
A promising method of the synthesis of carboxyl-containing epoxy oligomers with a
nonhydrolyzing ester bond is the interaction of phenol-containing epoxy oligomers with
formaldehyde and amino acids. Epoxy oligomers modified by polyfunctional phenols are
used as a phenol component. The reasonable cost and a sufficiently large choice of epoxyphenol oligomers open wide possibilities for producing film formers with a diverse set
of properties. In combination with hardeners from amino-, urea- or phenol-formaldehyde
resins, such oligomers are used in formulations of water-base materials for protection for
the internal surface of canning containers. Compositions are hardened for 212 min at
200215C to form coatings resistant to pasteurization and sterilization, the action of acids,
alkali and solvents. In industry, use is made of water-base materials based on epoxy oligomers modified by acrylates. One of the most widespread types of epoxyacrylic film formers
for aqueous systems is a mixture of epoxy oligomer and carboxyl-containing acrylate. Compositions are hardened in the presence of amino-aldehyde resin at 150370C to form a
high-quality coating resistant to the action of acids. Aqueous materials based on mixtures
of epoxy oligomers with acrylates do not always satisfy manufacturers of canning containers by their water and chemical resistance and other properties. Coatings based on epoxyacrylates with carboxyl groups in the side chains possess better performance parameters.
Water-base canning materials are produced using epoxyacrylates obtained by the reaction of epoxy oligomers or modified epoxy oligomers with carboxyl-containing acrylic
systems, in particular, film formers containing products of interaction of dianic epoxy oligomer with the mixture of methacrylic acid, styrene and epoxyacrylate. The dispersion is
hardened in the presence of hexamethoxymethyl melamine at 188C for 60 sec. The coatings are distinguished by high adhesion to aluminium and the resistance to hot water.
Carboxyl-containing epoxy oligomers and epoxyacrylates are of interest as potential
film formers for electrophoretic materials. In the USA, water-base compositions have been
developed, intended for anaphoretic coatings of the internal and external surfaces of cans.
The composition contains the reaction product of epoxy oligomer with carboxyl-containing

CHAPTER 7

239

acrylic copolymer. For hardening, phenol-formaldehyde resin or nitrogen-containing resin


are used. After neutralization by tertiary amines of the type of pyridine, morpholine, methyl
pyrrole etc., the composition is used for coating of drawn cans or rolled metal to be used
for the fabrication of composite cans. Coatings are distinguished by an increased elasticity.
A special place among water-base materials is occupied by compositions based on epoxy oligomers modified by phosphoric acid. Protection of canning containers by such materials makes it possible to provide for chemical and water resistance, strength and other
properties of coatings based on epoxyphenol lacquers. Hardeners for phosphorus-containing epoxy oligomers can be melamine-formaldehyde resins or their mixtures. Catalysts of
hardening are usually not used, because phosphoric acid present in the film former plays
the role of an inner crosslinking catalyst. Water-base epoxyphosphate compositions are applied to a metal support in one or two layers of the total thickness 0.002 mm and hardened
at 200C. The coating has a high resistance to hot water and solvents. Water-base materials
with the content of nonvolatile components up to 35%, based on phosphorus-containing epoxy oligomer having OPO(OH)2 groups, are used for protection of canning containers.
The coatings are distinguished by an increased resistance to sterilization and pasteurization.
The assortment of phosphorus-containing film formers for aqueous compositions is expanded due to the phasing in of epoxyphosphate oligomers modified by acrylates or their
mixture with other unsaturated monomers.
For painting canning containers, use is made of epoxy oligomers modified with polyesters and polyurethanes. Aluminium and steel beer cans are recommended to be painted
by an aqueous dispersion; the composition includes 70 95% of carboxyl-containing polyester based on trimellitic anhydride, adipic acid and 530% epoxy dianic oligomer. After
the neutralization with ammonia, the dispersion is applied to the inner surface of cans and
is hardened for 10 min at 200C. The coatings do not affect the taste qualities of the packaged product.
Epoxypolyurethane water-base materials for painting of the inner surface of beer cans
contain epoxy oligomer and polyurethane forpolymer, which is obtained by the interaction
of a mixture of polyester polyol and carboxyl-containing oligomer with polyisocyanate;
polyisocyanate plays the role of a crosslinking agent. Coatings are distinguished by chemical endurance, elasticity and good adhesion to metal.
Water-base materials based on acrylic resins are of interest for production of canning
containers with high durability, light permanence and heat resistance of coatings. However,
due to the negative effect on the taste qualities of products, pure acrylates are used mainly
for painting of the outer surface of containers and as coating lacquers for protection of lithographic printing. Compositions based on alkyl acrylates, methacrylic acid, methacrylate
and vinyl acetate are widely used for this purpose. Coatings based on these copolymers are
hardened at 200220C for 12 min.
Coatings based on vinyl materials are distinguished by a high corrosion resistance and
elasticity. However, owing to the insufficient thermal resistance they are unsuitable in the
cases when products are subjected to prolonged heat treatment. As film formers in vinyl
systems, use is made the most frequently of copolymers of vinyl chloride and vinylidene
chloride with acrylate or other monomers. Stable aqueous dispersions for protection of the
inner surface of metal cans for beer and drinks are obtained based on copolymer of vinyl
chloride and vinylidene chloride with vinyl monomers, which contain carboxyl or sulfonyl
groups. The most frequently used formulation of this type is based on copolymer from
3085% vinyl chloride, 1050% methyl acrylate, 0.120% acrylic acid and 0.57% vinyl
sulfonic acid. The inner surface of metal cans is protected by a water-base composition

240

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

based on a film former obtained by radical copolymerization of acrylic acid, ethylacrylate


and styrene in a mixture with cyclohexanone with butyl cellosolve, containing vinyl copolymer and epoxy oligomer.
Aqueous pigmented materials serve for exterior painting and lithography of cans. As
film formers, use is made of alkyd, polyester, acryl or epoxyphenol oligomers. Water-base
compositions for this purpose are obtained based on hydroxyl-containing polyester, which
represents the product of polycondensation of a mixture of fatty alcohols with a mixture of
cycloaliphatic, aromatic or aliphatic 1-, 2-, 3-basic carboxylic acids.
Water-base materials intended for painting of canning containers are applied to the
surface using rolls or by spraying. The choice of the application method is determined in
each particular case by the type of container and its fabrication process. In production of
multiply-drawn composite or two-piece cans, use is made of rolls or sheet metal painted
preliminarily on the standard equipment. Before formation of cans, the metal surface is
coated with a layer of lubricant, which facilitates the fabrication and protects the coatings
from deterioration. If necessary, one or two layers of material are applied by spraying on
the inner surface of composite cans. Two-piece cans fabricated by the ironing technology
are decorated from the outside and painted by spraying using two-nozzle sprayers or sprayers with nozzles displaced relative to each other, which makes it possible to apply a twolayer coating.

7.5

Modification of polyvinyl chloride compositions by thermoplastics

The use of regular-structure compounds as modifiers makes it possible to improve significantly the performance properties of coatings in biochemically active media. To improve
the performance properties of perchlorovinyl coatings, we studied the effect of various
physicochemical factors on the properties of block copolymers based on styrene and butadiene for their subsequent use to increase the adhesion and protective properties of perchlorovinyl systems for protection of canning containers.
The effect of the concentration of styrene in block copolymers on the properties of
coatings has been studied (Table 7.3).
Table 7.3 Effect of the concentration of -methyl styrene on the properties of coatings.
Concentration of

-methyl styrene
31.5
34.5
42.5
44.5
52.0
DMST-35

50

100

200

300

E0 /E,
E = 100%,
I = 1 min

1.47
1.87
2.55
2.21
5.37
2.18

1.60
1.98
2.59
2.35
5.29
2.17

1.76
2.12
2.70
2.65
6.04
2.21

2.04
2.52
3.47
3.74
8.95
2.59

4.76
4.76
3.71
3.85
2.70
4.55

Stress (MPa) at elongation, %

Maximum swelling
in isooctane,
%
132
136
105
110
81
126

Stresses characterizing the stressstrain properties of systems have been studied at


different degrees of strain. The maximal swelling of specimens in isooctane enables a
judgement of the density of the three-dimensional network of block copolymers. The rigidity of specimens was assessed by the relative change of the initial modulus to the value of
its change at a relative deformation of 100% for 1 min. It has been shown that, as the

241

CHAPTER 7

concentration of -methyl styrene in the block copolymer DMST increases, the rigidity of
specimens is observed to rise monotonically and the rate of the relaxation processes to decrease. The deformation properties of specimens are characterized by the value of stress at
a fixed elongation determined from the curve of the dependence of stress on the values of
strain. The rate of the relaxation processes was assessed by the inverse value of the relative
drop of the modulus in the process of relaxation at a constant elongation of 100% for 1 min.
Thermoelastoplastic specimens were swollen at room temperature in isooctane. The maximal swelling was achieved in 34 days.
These results are agree with the regularities in the change of internal stresses, from
which it also follows that as the concentration of -methyl styrene in block copolymers increases, internal stresses rise 23 times. A decrease of swelling of specimens is determined
by the increase of the density of the three-dimensional network with the increase of the methyl styrene content.
To study the particular features of structure formation in regular-structure polymers
depending on their chemical composition, use was made of the method of electron microscopy. Films were prepared from solutions of specimens in benzene at a concentration of
0.003 g/mm. Films were contrasted in vapours of osmium tetroxides.
Analysis of the data obtained indicates that thermo- and elastoplastics are two-phase
systems. Owing to the significant rigidity of polystyrene blocks, they interact one with another to form domains with parallel orientation of anisodiametric-type chains. With the concentration of styrene blocks rising, the size of the domains increases. The thickness of
polystyrene domains in the concentration range from 30 up to 50% is 3035 nm. Polystyrene domains interact to form networks, the cells of which comprise the elastomer part of
the compositions. The optimal properties of block copolymers, enabling their use as modifiers of perchlorovinyl compositions, are observed at 3035% polystyrene in the chain.

7.6

Effect of the structure of the block copolymer chain on the properties


of coatings

Thermoelastoplastics with the regular structure of the chain are characterized by higher
physicomechanical properties. The strength of films from thermoplastic DMST-35 in tension was 23.0 MPa, relative breaking elongation was 860%, the modulus at 50% was 2.1
MPa, p = 1.0 MPa.
Thermoelastoplastics with a similar ratio of irregular-structure components even after
introduction of a Zn atom into their chain and using various hardeners were distinguished
by lower physicomechanical properties (Table 7.4).
Table 7.4 Effect of the nature of the hardener on the physicomechanical properties of Zn-TEP.
Hardener

Initial composition
Altax+paraquinone dioxyl
Sulfur+chloxyl
Sulfur+santokur
Chloxyl
Diazo amino benzene

Deformation strength
f50, MPa

f100, MPa

10.6
9.5
10.5
9.8
9.1

13.7
14.3
12.4

12.6
12.0

p,
MPa

p, %

Adelam

20.0
18.8
16.4
13.8
18.0
16.8

202
195
188
95
246
229

3.3
0.6
0.7
1.1
0.9
0.9

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

It is seen from the table that for films from irregular-structure thermoelastoplastics the
values of elasticity, adhesion strength and breaking strength are considerably decreased.
Use of various oligomers (epoxyphenol, epoxyphenol acryl) and compositions on their
basis as modifiers makes it possible to increase the elasticity of coatings without significantly changing the strength parameters. Table 7.5 presents the data on the effect of various
modifiers on the mechanical properties of coatings from thermoelastoplastic Zn-TEP.
Table 7.5 Properties of modified thermoplastics.
Modifier
EF
EF1
EF2
EFA-2
EFA-2 + 5 wt.% acetur
EFA-2 + 10 wt.% acetur
EFA-2 + b-cyanoethyl acrylate
FP-326

f100, MPa

f200, MPa

fn, MPa

p, %

12.2
8.7
9.0
9.8
8.3
7.0
10.2
8.9

16.7
12.4
12.8
13.2
11.1
9.8
13.6
11.3

16.7
16.2
17.8
15.3
14.5
12.9
16.9
13.9

210
270
460
287
375
365
370
450

From the analysis of the table data, it follows that modification of butadiene styrene
compositions by epoxyphenol compositions makes it possible to improve the physicomechanical properties of coatings (strength, elasticity). However, the adhesion strength of
irregular-structure copolymers is more than 3 times as low as for block copolymers with
the similar ratio of regular-structure components.
For this reason, further studies were carried out using regular-structure block copolymers as modifiers.

7.7

Development of the method for improving the protective properties


of polyvinyl chloride compositions by modification with block
copolymers

Block copolymers are widely used in developing polymer materials of various purposes.
This is due to the fact that they are characterized by a single-phase ordered structure. The
size of structural elements, their morphology, and, therefore, the properties of polymers can
be regulated within broad ranges by changing the length, chemical composition, molecular
mass of particular blocks.
In this connection, we used regular-structure block copolymers as modifiers to improve the biochemical resistance of perchlorovinyl (PVC) coatings.
A characteristic feature of perchlorovinyl coatings is that they possess a high weatherability, resistance to the action of acids, strength and plasticity. At the same time, they
dissolve poorly in organic solvents, which is accompanied by the formation of an inhomogeneous imperfection structure and low strength of adhesion to various materials. To improve the structure and properties of the coatings, 1025% solutions of PVC are
supplemented with plasticizers and various modifying additives.
The most widespread components in fabrication of compositions are mixtures of various solvents: ethyl acetate and butyl acetate, ketones, chlorinated lower aromatic and aliphatic hydrocarbons.

CHAPTER 7

243

Dibutyl phthalate, tricresyl phosphate, sovol (polychlorobiphenyl) are used as plasticizers. An increase of the heat resistance of protective coatings is performed by way of introducing various stabilizers, in particular, epoxidized oils (soybean, sunflower), lowmolecular-mass epoxy oligomers. They serve as acceptors of HCl, which is evolved in the
decomposition of a polymer.
For regulation of the structure and properties of polyvinyl chloride coatings, used was
made of divinyl styrene thermoelastoplastics, which are distinguished by the nature of the
end groups (styrene and -methyl styrene), the structure (linear and branched), by various
contents of polystyrene blocks, as well as the ones with different molecular masses.
Coatings were formed both from solutions of PVC compositions and from powder systems.
The characteristics of thermoelastoplastics used in the formation of coatings from
powder systems is given in Table 7.6.
Table 7.6

Characteristics of thermoelastoplastics.
Melt
Hardindex
ness
f0 T = 90C,
Tensile
Relative
216 H,
strength, elongation,
g/10 min
MPa
%

Name

Chemical formula

Content
of polystyrene

Divinyl--methyl styrene
DMST-30L
Divinyl--methyl styrene
DMST-30-R
Divinyl styrene DST-30L1
DST-30L2
Divinyl styrene DST-20-R

P-2MS-PB-P--MS

30

31.5

890

68

51.5

Si-PBP-2MS

30

28.5

855

65

39.0

PS-PB-PS
PS-PB-PS

28
28
20

144.0
255.0
159.0

935
847
760

66
66
50

48.0
24.0
31.0

DSG-30-R
DST-50-R

(PS-PB)4Si
(PS-PB)4Si

31
50

211.0
105.0

910
765

70
89

37.0
48.1

Si

Physicochemical
characteristics

Based on the performed studies, it has been found that the best set of performance
properties is observed in modification of perchlorovinyl compositions using as modifier
-methyl butadiene styrene DMST-30L or DMST-35L in the presence of plasticizer
PPA-7.
Table 7.7 presents the physicomechanical properties of coatings produced at various
ratios of the main components polyvinyl chloride (PVC), block copolymer thermoplastic
DMST-35L and plasticizer (polypropylene glycol).
The stressstrain properties of films from mixture compositions were studied at an extension rate of 25 mm/min.
It is seen from Table 7.7 that the dependence of breaking strength on TEP concentration is nonmonononic. First, as the concentration of TEP is increased up to 50%, it goes
down sharply, and then at a further increase in the content of TEP it increases, staying lower
than the strength of the initial PVC and TEP components. The elasticity modulus increases
with the increase of the concentration of PVC. The ratio of the ingredients in the composition has a significant effect on the value of internal stresses. The results of the study are
presented in Table 7.8.

244

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Table 7.7 Deformation/strength properties of modified polyvinyl chloride films.


Composition
TEP

PVC

PPA

0
25
25
50
50
50
50
50
50
50
70
100

100
75
75
50
50
50
50
50
50
50
30
0

0
0
25
0
10
20
25
30
50
70
0
0

E at = 50%, GPa

p, MPa

p, %

9.8
14.6
12.0
10.8
9.6
5.3
4.9
5.3
2.1

55.4
15.7
15.9
5.9
6.8
6.1
6.2
5.2
2.9
2.4
15.7
23.0

52
22
132
366
77
157
157
128
113
105
1070
860

Table 7.8 Effect of the ratio of individual ingredients on internal stresses in the formation of films
from mixture compositions.

p, MPa

Composition
TEP

PVC

PPA-7

0
25
25
50
50
50
50
50
50
50
70
100

100
75
75
50
50
50
50
50
50
50
30
0

0
0
25
0
10
20
25
30
50
70
0
0

18.0
10.5
0.9
2.4
2.1
1.1
1.0
0.9
0.9
0.7
1.1
0.9

It is seen from the table that significant internal stresses occur in films from PVC. Introduction of thermoplastics decreases them more than 1.5-fold at a TEP content of 2%. The
most sharp decrease of internal stresses, more than 8 times, is also observed at an increase
of the concentration of TEP up to 50%.
The further decrease of internal stresses was performed by introducing the plasticizer
PPA-7.
Also noteworthy is a sharply increased adhesion of coatings from modified PVC,
which was 180200 MPa, whereas films from nonmodified PVC peel off at critical internal
stresses of 1.41.6 MPa.
As the concentration of the plasticizer in the mixture is increased, internal stresses go
down. For films from a mixture composition with the PVC to TEP ratio of 50:50, internal

245

CHAPTER 7

stresses decrease by about 2 times at a plasticizer concentration of 20%. The further increase of plasticizer concentration has no significant effect on the value of internal stresses.
Their sharp (3-fold) decrease is found to occur at a plasticizer concentration of 70%.
The effect of the plasticizer concentration of the adhesion properties of compositions
was studied by the peeling method at a testing rate of 575 mm/min.
Table 7.9 presents the data on the adhesion strength of coatings with the 50:50 ratio of
the components (PVC:TEP) as a function of the concentration of plasticizer (PPA-7).
Table 7.9
PVC/TEP ratio

Content of plasticizer PPA-7, wt. %

Adhesion strength, MPa

50/50
50/50
50/50
TEP

20
30

0.445
0.350
0.345
0.221

It is seen from the table that introduction of a plasticizer up to 2030 wt. % has no
significant effect on the adhesion strength of modified polyvinyl chloride specimens.
The change of the ratio of the ingredients renders a significant effect not only on the
rate of the relaxation processes in the formation of coatings from mixture compositions, but
also on the relaxation processes in formed coatings in their operation.
The rate of the relaxation processes in formed coatings from mixture compositions was
assessed at different temperatures by the change of the elasticity modulus at a constant load
in 10 and 100 sec. The relaxation coefficient
E ( 10 sec ) E ( 100 sec )
K = ------------------------------------------------------------- 100% .
E ( 10 sec )
The results of the study are presented in Table 7.10, E in 103 MPa.
Table 7.10 Effect of the ratio of PVC and TEP in mixture compositions on the film relaxation
constant at different temperatures.
TEP/PVC

100/0
70/30
50/50

Parameters

E = 30%
Kp
E = 30%
Kp
E = 30%
Kp

Temperature, C
20

30

40

50

60

43.5
9.0
90.9
13.2
191.0
14.4

40.5
10.7
82.2
16.4
172.0
16.3

37.7
13.4
74.9
20.4
156.0
21.0

34.8
20.2
66.8
26.4
143.0
29.0

29.8
19.1
57.1
36.2
122.0
37.8

It is seen from the table that the rate of the relaxation processes increases for films from
all compositions with the temperature increasing. At the same time, the rate of the relaxation
processes also significantly rises with the increase of the content of PVC.
Comparison of these data with the results of the study of internal stresses as a function
of the concentration of PVC in mixture compositions indicates the absence of their

246

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

correlation, because internal stresses increase significantly due to the retardation of the relaxation processes in the formation of coatings with the content of PVC increasing.
Using the method of electron microscopy, it has been found that the specific change
of the relaxation characteristics depending on the ratio of ingredients in mixture compositions is due to the features of structure formation in the fabrication and operation of coatings.
In studies of the structure of coatings from PVC by the method of electron microscopy
it has been found to be inhomogeneous by the size of globules, which change within the
range of 3080 nm.
The structure of the block copolymer of -methyl styrene thermoplastic is characterized by the occurrence of domain-morphology structural elements with the domain width
of 20 nm.
At a 30% content of PVC, the composition is found to have a more homogeneous globular structure with the structural elements of 2550 nm in size. An increase of the concentration of PVC up to 50% significantly increases the inhomogeneity of the structure. The
structural elements of PVC are distributed in the film unevenly in the form of aggregates
0.20.3 m in diameter. A further increase of the concentration of PVC up to 75% increases
the inhomogeneity even more. Separate regions of structural elements characteristic of PVC
and TEP are observed.
The distribution of ingredients in mixture compositions was regulated by introducing
a plasticizer.
Thus, at a PVC to TEP ratio of 30:70, one observes a good match of ingredients on the
level of their supramolecular structure. Production of coatings with the homogeneous structure and a good match of ingredients on the level of supramolecular structures can be done
in the presence of a plasticizer at a PVC to TEP ratio of 50:50.
It follows from these results that the rise of the relaxation constant for films from mixture compositions with the PVC concentration increasing is due to the worsening of the
compatibility of components on the supramolecular level and the formation of a defect
structure more readily destroyed under the action of an applied load.
Based on the results of these studied, compositions containing 50% PVC and 50%
thermoelastoplastics with an optimal concentration of the plasticizer were chosen, which
provide for the fabrication of coatings with the best protective properties.

7.8

Studies of the relaxation properties of coatings from polyvinyl chloride


compositions modified by thermoplastics

The relaxation properties of coatings were assessed by studying the temperature dependence of the stressstrain properties of compositions at an optimal ratio of PVC/TEP =
50:50 and different contents of plasticizer PPA-7. The tests were carried out at an extension
rate of 25 mm/min within the temperature range of 2080C.
The results of the study are presented in Table 7.11.
Figure 7.1 presents a temperature dependence of strength and relative breaking elongation on the testing temperature. Analysis of these results suggests that the resistance to
rupture and breaking elongation decreases at an increase of temperature for nonplasticized
specimens.
For plasticized specimens, p changes nonmonotonically depending on the concentration of plasticizer. An exception is the initial composition, for which the maximum in the
change of p is not observed.

247

CHAPTER 7

70

p, %

60
1

p10, MPa

50

400

40

300

30
4

200

20
4

10

10

30

100

50

70

10

90

30

50

70

T, C

90
T, C

Figure 7.1 Dependence of strength (a) and relative elongation (b) on testing temperature for specimens plasticized with PPA-7 and nonplasticized specimens of coatings. a: 1, no PPA-7; 2, 10 wt. %
PPA-7; 3, 20 wt. % PPA-7; b: 1, no PPA-7; 2, 10 wt. % PPA-7; 3, 20 wt. % PPA-7; 4, 30 wt. %
PPA-7.

Table 7.11 Effect of the testing temperature and the concentration of plasticizer on the
physicomechanical properties (tensile strength p, ultimate elongation p).
Concentration of
PPA-7, wt. %

Properties

p, MPa
p
p, MPa
p
p, MPa
p
p, MPa
p

10
20
30

Testing temperature, C
20

35

50

65

80

5.9
370
6.8
93
6.1
180
5.2
146

5.3
340
5.6
134
3.8
250
3.0
142

4.2
352
3.1
283
2.3
246
2.0
175

3.3
277
1.0
245
1.1
214
0.9
156

1.7
134
0.5
165
0.6
155
0.5
143

To elucidate the mechanism of interaction of the components in a modified polyvinyl


chloride system, the activation energy of the breakdown process was calculated.
It is known that the tensile stress calculated for the real transverse cross section of a
specimen at the moment of rupture [p = Pp (E + 1)] changes for many polymers, depending
on temperature, according to an equation similar to the Arrhenius equation:
p = BeU/RT,
where p is the rupture stress, B is a constant, R is a gas constant, T is temperature in degrees
Kelvin and U is activation energy.

248

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

logp

2.6

2.2
2
1.8

3
4

1.4
1.0

2.8

3.0

3.2

3.4

1000/T, K

Figure 7.2 Dependence of breaking stress in the logarithmic coordinate on inverse temperature for
specimens with different concentrations of plasticizer PPA-7 obtained from solutions. 1, 0 wt. %
PPA-7; 2, 10 wt. % PPA-7; 3, 20 wt. % PPA-7; 4, 30 wt. % PPA-7.

In (log p 1/T) coordinates, this dependence has the shape of a straight line, whose
slope to the abscissa axis is proportional to the activation energy.
Figure 7.2 presents a dependence of log p on 1000/T for four systems studied. This
dependence is seen to be not linear but to present a jogged line in the temperature range
studied (2080C). The inflection points of these lines are in the temperature range of
4550C. An exception is the initial system, for which this point is at 60C.
The fact that the dependence of log p on inverse temperature for the compositions
studied is a jogged line suggests that, depending on the temperature range of studies, the
breakdown of modified polyvinyl chloride compositions is determined by different mechanisms characterized by their own activation energies. In turn, these regularities are determined by the different character of structure formation and the level of match of the
components at the impact of temperature.
Table 7.12 gives the results of calculating the activation energy for the systems studied.
Table 7.12 Effect of the concentration of plasticizer on the activation energy of modified polyvinyl
chloride compositions at different testing temperatures.
Concentration
of plasticizer

0
10
20
30

Testing temperature range within which the dependence


log p 1/T is linear
2050C U1, kcal/mol

5080C U2, kcal/mol

2.29
1.22
3.23
6.01

8.85
8.92
6.16
6.38

It is seen from the table that at higher temperatures (5080C) the activation energy
is larger than at decreased temperatures (2050C).

249

CHAPTER 7

The differences in the activation energies are smoothed with temperature increasing,
and at 30 wt. % of plasticizer the values of U1 and U2 are almost equal. Similar regularities
in the change of activation energy depending on the testing temperature were observed for
specimens obtained not by forming films from solutions, but by calendering a mixture of
PVC with modifier TEP.
The results of the tests of the mechanical properties of this composition are presented
in Table 7.13.
Table 7.13 Mechanical properties of PVC modified by TEP.
Parameter

Testing temperature, C
20

f30, MPa
p, MPa
p, %

7.26
9.90
90.0

30
5.71
8.39
106.0

40
3.97
6.39
126.0

50
2.55
4.56
143.0

60
1.65
3.08
123.0

70
1.16
2.10
118.0

80
0.80
1.36
116.0

It is seen from the table that for this batch of specimens, also with the testing temperature increasing, the resistance to rupture decreases monotonically, and the breaking elongation passes through a maximum revealed at approximately 50C.
The processing of experimental results with the view to determine the activation energy of the breakdown for this composition again showed a similar character of the dependence of log p on inverse temperature in the shape of a jogged line, whose inflection is at
about 45C (Fig. 7.3). The values of the activation energy calculated by the slope of, respectively, the gradual and steep segments of this jogged line are 2.7 and 10.3 kcal/mol.
From the analysis of the results of the studies, it follows that the formation of modified
perchlorovinyl compositions at a temperature of 4060C is accompanied with a significant increase of the intermolecular specific interaction between structural elements and an
improvement of performance properties of coatings.

7.9

Modified perchlorovinyl coatings with increased shelf-life

Coatings based on perchlorovinyl compositions are characterized by a valuable set of properties. The most important of them are weatherability and the possibility of preserving the
protective properties in operation under conditions of the action of organic and inorganic
acids.
However, under operation conditions, owing to the imperfection and inhomogeneity
of their structure, the service life of coatings does not exceed 23 years.
To improve their protective properties and to increase durability, structure formers are
proposed to be used as modifiers; they increase the adhesion strength and stability of adhesion of coatings to metal in contact with elements, water, and high-humidity atmosphere.
To increase the adhesion/cohesion strength and protective properties of coatings based
on perchlorovinyl compositions, use is made of modifiers containing coordination organic
compounds with plane-oriented structure and coordination ions of various metals in macromolecules. These compounds increase the adhesion strength 23-fold and simultaneously improve the protective properties of coatings in aggressive media.
However, due to the complexity of their synthesis, they have not found wide use in
industry. Because of this, compounds with various functional groups are used as modifiers

250

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

log p
2.6

2.2

1.8

1.4
3.0

3.2

3.4

1000/T, K

Figure 7.3 Dependence of the logarithm of the breaking stress on inverse temperature for TEPmodified PVC specimens obtained by calendering of the mixtures. 1, U = 2.7 kcal/mol; 2, U = 10.3
kcal/mol.

contributing to the increase of the adhesion strength of coatings from resin based on chlorinated polyvinyl chloride resin PSKh-LS and its stabilizers in operation in liquid media.
The adhesion strength was measured by the method of irregular peeling of coatings
applied to plates from low-carbon steel 08kp, at a peeling rate of 2.4 mm/min.
Holding of coatings in a medium significantly reduces their adhesion strength. After
their removal from a medium, specimens were held for 24 h at 20C, and their adhesion
was measured. At a small exposure in the medium, the adhesion of coatings is partially restored. An irreversible decrease of adhesion strength is due to the uneven distribution of
adhesion bonds in the boundary layers of the coatings due to the inhomogeneity and imperfection of their structure, which leads to the development of corrosion processes.
The level of the recovery of the adhesion strength is significantly affected by modifiers. Owing to the larger surface energy and the presence of active functional groups, modifiers are adsorbed in the boundary layers of coatings to improve their physicomechanical
properties. Modifiers were introduced in an optimal amount of 12% to the resin prior to
the application of coatings. Table 7.14 presents the data on the effect of the time of exposing
Table 7.14
Medium

Distilled water

HCl, 5%

H2SO4, 5%

Exposure, min

0
10
40
60
0
15
30
0
15
10

Adhesion, g/cm
initial

after exposure

recovered

% of recovery

333
333
333
333
304
304
304
312
312
312

92
31
0

36
0

12
10

185
59
0

157
96

99
53

55
17
0

51
31

31
16

CHAPTER 7

251

coatings to different media on the adhesion strength of the initial coatings after holding
them in media and the restored strength.
The effect of modifiers on the adhesion strength of perchlorovinyl coatings was studied. As additives, used was made of alkoxysilanes A-2 and ASOT-2 containing various
functional groups, additions of MHU and PMHU containing hydroxyl and ester groups,
regular-structure aromatic stabilizers with active radicals of CPA.
The results of studies of the adhesion strength of perchlorovinyl coatings are presented
in Table 7.15.
Table 7.15
Modifier

A-2
CPA
MHU
PMHU
ASOT-2

Adhesion strength, g/cm


310
680
325
295
295
550

35
15
75
15
15
25

It is seen in the table that additions of CPA, MHU, PMHU change little the value of
the adhesion strength of perchlorovinyl coatings. Additions of MHU, PMHU decrease the
adhesion strength as compared with this parameter for nonmodified coatings.
Modifiers A-2 and ASOT-2 increase approximately twofold the adhesion strength of
initial coatings prior to the action of aggressive media on them. However, after keeping the
coatings in liquid media, probably, due to the ability of alkoxysilanes to be hydrolyzed under these conditions, the adhesion strength of the coatings decreases.
At the action of electrolytes, the highest adhesion strength is observed for perchlorovinyl coatings modified by antioxidant CPA.

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8
8.1

Ways of Modifying the


Properties of Metallized
Packaging Materials

Purpose and fields of application

Articles from plastics, ceramics and composite materials with metallized surface are used
at present in many industries and are widespread in households. The low specific mass,
good mechanical parameters, the absence of corrosion problems make it possible in a number of cases to give them the preference over traditional metals.
Abroad, metallized film materials are widely used in fabrication of various packagings
in food industry and other industrial spheres. This is due not only to the improved decorative
properties of packaging materials in metallization, but also a significant (several orders of
magnitude) reduction of vapour permeability and an increase of the barrier properties of
combined films.
New applications of synthetic materials (automotive industry, production of household appliances and electronics, etc.) put forward increased demands to their appearance
and service life. In this connection, a topical problem are the specific properties of the surface of such materials, whose purpose is to conceal the formation defects, to increase the
resistance to cracking, scratching, as well as atmospheric and chemical endurance, to improve the decorative properties. There are two ways of finishing nonmetal materials metallization and painting with lacquer-and-paint materials.
Metallized dielectrics, whose surface is partially or totally coated with a metal, possess
an increased resistance to the action of organic solvents, moisture, boiling and high temperatures; have high physicomechanical and decorative properties, as well as can endow articles with specific properties (for instance, metallized coatings in electronics are used to
shield the bodies of equipment from interference noise, for elimination of statics, protection
from the impact of various short-wave radiations). For metallization of dielectrics, such
metals are used as aluminium, copper, nickel, platinum, tin, lead, zinc, iron etc., as well as
metal alloys. The choice of a metal is determined by the purpose of a metallized item and
the technological features of the metallization method.
In finishing the surface of dielectrics with lacquer-and-paint materials, there are a
number of problems related to the adhesion strength of coatings to plastics, a relatively low
resistance of plastics to the action of increased humidity, high temperatures and organic solvents, as well as to the provision of the required decorative, physicomechanical and adhesion properties.
To endow articles from nonmetal materials with high decorative and performance

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properties, a promising way is to combine two methods of surface finishing to produce a


combined coating: by applying a metal layer and by colour printing. In this case, besides
the decorative properties, metal endows an article with an increased resistance to the action
of high temperatures, moisture, organic solvents, as well as hardness and wear resistance.
A lacquer-and-paint material can not only be used to provide for high decorative and
performance properties, but protect the metal film from oxidation. Besides, a metallized
coating enables the use of electrodeposition for painting various dielectrics (polymer films,
plastics).
Electrodeposition of water-base lacquer-and-paint materials is one of the most widespread methods of producing single-layer and primer coatings on metal articles under conditions of large-series production. This method conforms the most completely to the
requirements imposed on the modern conditions and processes of chemical technology, is
a practically closed technological cycle with total automation and mechanization of the production process.
However, many problems associated with the use of the electrodeposition method for
painting of metallized dielectrics have not been solved. The particular features of forming
coatings on a metallized sublayer have not been sufficiently studied in painting by the
electrodeposition method, the chemical nature of the surface of the metal support and the
structure of the surface of the metallized layer have a significant effect both on the technological regimes of the process and on the structure and properties of protective coatings.
Recently, to increase the corrosion resistance of steel, Western companies in various
machine-building industries make use of steel workpieces with various kinds of galvanic
coatings, mainly zinc nickel, zincaluminium, nickelcadmium, chemical or galvanic
nickel followed by the application of protective lacquer-and-paint materials.
A large cycle of works is under way in solving the problem of decreasing the hardening
temperature and time of materials manufactured by Russian industries. The main waterbase compositions, which can be applied to metallized film materials, harden at 180C.
Works in this field are carried out in several directions based on the introduction of
hardening catalysts, special low-temperature hardeners, into film formers, as well as by synthesizing bonding adhesives with the low temperature of hardening.
Such additives include siccatives of metals, organic accelerators, modifiers based on
epoxy and isocyanate oligoesters. Usually, a significant drawback of such additives is a decrease of the stability of performance properties of the working solutions of polymer compositions prior to their application and, respectively, a deterioration of the properties of such
coatings.

8.2

Methods of forming metallized layers on polymer materials

The performance properties of metallized polymer materials with a protective lacquer-and-paint coating should be determined first of all by the adhesion of the metallized
sublayer to the polymer film and protective coating to metallization.
At present, three groups of methods are used for metallization in Russian and Western
industries:
mechanical (conformal coating, hot embossing);
physical (gas-thermal deposition of melted metal and metallization under vacuum);
chemical (chemical and chemico-galvanic metallization).
Some results of using various methods of metallization in this country are given in
Table 8.1.

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255

Table 8.1 Effect of the method of metallization on adhesion of coatings.


Metallization method
Chemical
Chemico-galvanic
Vacuum

Metallized dielectrics

Type of coating

Almost all kinds of plastics,


ceramics
ABS plastic, polystyrene,
polypropylene, polysulfone,
glass fibre
Polyamide, aminoplastics,
epoxides

Copper, nickel,
silver
Copper,
chromium, nickel,
lead, silver, tin
Aluminium,
copper

Total thickness Adhesion


of coating, m
0.0110

Good

3065

High

0.11

Low

Under conditions of series production, the most widespread methods of metallization


of complex-shape items are chemical methods.
The method of chemical metallization by precipitation from solution consists in the
formation of a metal coating on the surface of a polymer material owing to the autocatalytic
chemical reactions at the interface. Before metallization, articles are subjected to activation
with the view to apply the catalyst of the reduction reaction of the base metal on the surface
of the support.
The process of chemical metallization is used the most frequently in coppering and
nickeling. The use of other metals is limited by the low stability of their solutions.
Activation can be performed according to two protocols: sensitization and direct activation. In sensitization, articles are first subjected to treatment in acidic, alkaline or alcoholic solutions of divalent tin salts. After the treatment, the surface is activated by solutions
of salts or complex compounds. Usually, acidic solutions of palladium chloride or alkaline
solutions of silver nitrate are used for this.
For direct activation, use is made most often of combined solutions containing tin and
palladium salts and solutions of accelerators. Accelerators used the most are solutions of
mineral acids, alkali and salts of alkaline metals.
The process of chemical metallization proper is performed in solutions containing the
salt of applied metal, the reducer, the complex former for binding ions of reduced metal into
a complex, buffer additions to regulate pH of the solution, stabilizers, gloss formers, etc.
For coppering, use is made of solutions containing copper sulfate, a complex former
(potassiumsodium tartrate, glycerol, etc.), a reducer (formaldehyde).
Nickeling is performed in acidic or alkaline solutions of nickel chloride or sulfate; layers of reducer 0.0110 m thick are usually applied, which are then reinforced by applying
a thicker layer of metal by a galvanic method.
Deficit and high cost of precious metals were the reason for developing the activation
processes without using palladium or with its decreased content in activating solutions.
To decrease the concentration of palladium in solution, it was proposed to treat the surface in sols based on silicon or iron oxides before the activation stage.
This treatment results in the creation of a developed surface, which significantly decreases the energy of the formation of active sites of palladium and its consumption. This
process is used in the metallization of printed circuit boards.
A method was developed of forming a catalytically active copper film by reducing its
hard-to-dissolve compound on a metallized surface by such efficient reducers as formaldehyde and hydrazine. The process proceeds in two stages: first the copper(I) oxide is formed
in a hydrazine medium, then a catalytic copper film is formed in a formaldehyde medium.

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A method has been proposed of activating dielectrics in solutions, which represent a


stable colloidal system consisting of salts of basic metals with complexons. Reduction of
sorbed ions is performed using boron hydrides of alkaline metals or their derivatives.
Methods have been developed of substituting activated solutions based on palladium
for solutions of sodium boron hydrides containing organic solvents (monobasic alcohols,
hexachloroethane, dimethylformamide etc.) for chemical nickeling of small items with increased adhesion of applied coating.
To increase adhesion of copper to polymers, the surface is activated by application and
subsequent thermolysis of copper hypophosphite. The surface is first treated with a solution
of thermosensitive copper salt. The subsequent heat treatment at 100140C leads to the
formation of metal copper particles, which are initiators of chemical precipitation of copper
from solution instead of palladium particles.
Chemico-galvanic metallization of dielectrics is widely used in formation of currentconducting layers of a sulfide coating. The method consists in the subsequent treatment of
the surface in a solution of copper salts and in a solution of a sulfonating agent, for instance,
sodium sulfide. Treatment with water leads to the hydrolysis of the copper salt and to the
sorption of partially soluble hydrolysis products on the surface. In the subsequent treatment
in a solution of the sulfonating agent, the copper-salt hydrolysis products are converted to
copper sulfide.
Electrical conductivity of copper-sulfide layers can be regulated by their multiple application, after which the cycle is repeated several times.
An increase of electrical conductivity of the coating is also achieved by adding copper
salts, zinc salts, metal copper or monovalent copper compounds to the solution.
To provide for the subsequent application of nickel by the galvanic method, the electrical resistance of the current-conducting sulfide layer should not exceed 103 Ohm/m.
A significant advantage of this method is the stability of solutions and properties of
the produced current-conducting layers due to the use of separately stable solutions of copper salts and the sulfonating agent, as well as to the removal of hydrolysis products (copper
salts), not bound to the surface, by washing.
The metallization process of dielectrics and the quality of metallized material are affected by the surface preparation. The quality of metallized material is determined by the
strength of adhesion of the metal coating to the polymer film, so the process is carried out
under conditions providing for the maximal and uniform strength of adhesion interaction.
Several theories explain adhesion of the metal layer to polymer. The theory of mechanical engagement pays main attention to the geometry of the surface. Adhesion is associated
with the number of micropits on the surface of well-etched polymers, into which deposited
metal penetrates. This theory explains well the formation of a strong bond of metal to heterogeneous-structure polymer, from the surface of which one of the phases is easily removed during the etching. For ABS block copolymers, these are globules of polybutadiene;
for polypropylene and polyethylene, the amorphous phase. In accordance with these views,
the force of adhesion of metal to polymer depends on the content of the phase easily removed in etching and its strength on the whole.
Chemical theory assumes the influence of the nature and concentration of functional
groups, for instance, the adhesion of a sulfite coating to chemically iodified polystyrene.
Wettability theory (surface-energy theory) considers adhesion as the adsorption process, in which the forces of attraction depend on the distance between two plane bodies,
i.e., the complete mutual wettability specifies a better adhesion.
Diffusion theory assumes an increase of adhesion as the result of the diffusion of one

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257

substance into the other. The diffusive character of the formation of the copper sulfide layer
enhances its adhesion properties.
According to electrostatic theory, adhesion is also affected by electrochemical reactions occurring near the interfaces between the polymer and working solution in the process
of metallization.
Thus, adhesion of the metal coating to the polymer film is affected by the state of the
surface and the strength of the polymer film, the presence of active functional groups on its
surface, its roughness, the nature and conditions of precipitation of the metal coating.
An optimal state of the surface of the polymer film before metallization depends both
on the method of processing the polymer into the film and the production of combined materials, and on the surface preparation processes, which include mainly degreasing and etching.
Degreasing is the initial stage of surface preparation to remove all organic impurities
possessing a large affinity to polymer. Most polymers are not wetted by water; therefore,
depending on the physicochemical properties of polymers, degreasing is done using organic
solvents or solutions of surfactants. Pure organic solvents are used rarely, because most of
them cause swelling of polymers, make the process more expensive and are harmful for the
environment. Commercially, aqueous emulsions are used the most; their compositions include organic solvents and synthetic emulsifiers. For degreasing, acidic or alkaline solutions of the type of KM-1 are also used. Besides the removal of contamination, this
treatment causes a change of the structure of the surface layers of polymers owing to their
partial dissolution and swelling. This increases the etching capability of polymer and makes
it possible to increase adhesion of coatings.
Most polymers are etched using chrome mixtures. The regime and composition of
etching solutions for particular polymers are found experimentally, taking into account the
grade of polymer, fabrication conditions, roughness and other factors.
Processes occurring on the surface of ABS resins during the etching in a solution of
chromic anhydride and sulfuric acid have been studied. Under the action of etching solutions, butadiene is oxidized by the double bonds to form carboxyl groups at a depth of several micrometres. Herewith, butadiene dissolves to form pits of the shape of spherical
micro- and macrocavities.
An important role is also played by the composition of the polymer matrix. Owing to
the presence of acrylonitrile in the structure of ABS polymer, a better hydrophilicity of the
surface is achieved than in polystyrene, which has no polar component in its structure.
Another etching mechanism is observed using organic solvents. For this block copolymer, particles of polybutadiene are embedded into the structure of styrene acrylonitrile and
swell to a greater extent than styrene acrylonitrile. Precipitation of metal occurs by the defects emerging under the action of internal stresses determined by the different extent of
swelling and deformation of separate fragments of the polymer chain in the block copolymer.
During the metallization of modified polypropylene subjected to etching, the quality
of the metal coating was shown to depend on the value and character of the distribution of
stresses in the surface layer, the extent of crystallization and size of supramolecular structures before and after the etching.
The use of minor amounts of finely dispersed additives and special surfactants has an
effect on the structural transformations during the etching, the stressed state on the surface,
amount and distribution of the amorphous phase, makes it possible to provide for the high
quality of coatings.

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Processes of etching some polymers in solutions containing no chromium compounds


have been developed. To ensure adhesion of the metal coating to polyamide, the material
is subjected to etching in aqueous solutions of organic bases (ethylene diamine and monoethanolamine), and then is treated in a solution of potassium hydroxide.
Polyethylene and polyamides are recommended to be etched in acidic or alkaline solutions of potassium permanganate.
In view of more rigorous ecological requirements, there is a tendency of using more
ecologically pure methods of modifying the surface of polymers, such as plasma etching,
corona discharge treatment, oxidative action of ozone and UV radiation.
In the preparation of the surface of polyethylene for metallization, it is efficient to use
combined methods, for instance, etching with a chromium mixture or with an acidic solution of potassium permanganate followed by the treatment with an electric discharge. High
adhesion of metallization in this case is explained by a favourable combination of the chemical and microgeometrical structures of the film surface.
The effect of the nature of the support with the general tendencies preserved has its
own features for various polymer film-forming systems. There is no data in the literature
on the effect of the nature of metallized support on polymer coatings formation. In this connection, for the development of polymer compositions and processes of their application to
metallized film materials, it is necessary to carry out studies to understand the mechanisms
of forming polymer coatings on metallized film materials and to develop methods of increasing the adhesion strength of coatings to nonpolar and weakly polar film materials.
Polymer systems have a low adhesion strength to nonpolar or weakly polar film combined packaging materials. Such materials also include metallized combined films.
A way of protecting the metallized layer from powdering under the action of a mechanical load and boiling is to form a thin polymer coating several micrometres thick on its
surface. To create such coatings, it is necessary to develop the physicochemical methods of
producing protective layers with high adhesion strength and resistance to sterilization.
The aim of the present work was to develop methods of modification of polymer compositions with high protective properties for metallized combined materials.

8.3

Protective coatings for metallized materials

High adhesion properties and resistance to the action of aggressive media are characteristic
of coatings based on low-molecular-mass epoxides ED-16 and ED-20. In this connection,
the epoxy bonding adhesive is chosen as the main component in developing a lacquer composition for protection of metallized packaging materials.
Studies of the regularities of forming the structure of epoxy network polymers contribute to the rational approach to monitoring the technological process for production and processing of polymer materials on their basis, because the formation of these polymers occurs,
in contrast with linear ones, in the hardening of coatings.
Network (cross-linked, three-dimensional) polymers, according to the definition given
well back by Schtaudinger, are high-molecular-mass compounds, in which the constituent
chains are linked in three directions by chemical bonds, from which, however, covalent
bonds are capable of forming a three-dimensional network structure.
Other types of interaction (ion, coordination, hydrogen or intermolecular) introduce a
significant and sometimes even prevailing contribution to the formation, structure and properties of the polymer network.

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259

The occurrence of chemical bonds specifies a distinctive feature of network polymers


their insolubility in organic solvents and infusibility. The significant role of physical
bonds in the formation of the three-dimensional network of thermoreactive polymers is indicated by the reversible change of the properties in repeated heating and cooling.
Based on the performed studies, it has been found that real network epoxy polymers
represent systems inhomogeneous by the size of structural elements, by the distribution of
chemical and physical bonds.
Epoxy oligomers consist of structural elements of globular morphology already in the
liquid phase. During the hardening, their polymerization proceeds first inside the globular
structures, which represent complex supramolecular formations consisting of more fine
structural elements.
Then links between these structures are formed. Chemical and physical bonds are distributed in the system unevenly. About 70% of them are formed inside the supramolecular
structures, which are characterized by a denser packing and orientation of polymer chains.
With this taken into account, the physicomechanical and protective properties of network polymers are by several orders of magnitude lower than their calculated values obtained with account for the strength of chemical bonds evenly distributed in the system.
Data of electron-microscopy studies of structure formation in hardening of network
polymers, including epoxy ones, also support the formation of an inhomogeneous defect
structure of the network, in which aggregates of colloidal size are separated by a structure
of lower-molecular-mass fractions.
Analysis of experimental data of the structure of epoxy coatings indicates that the
structural organization of polymers should be divided into three levels: molecular, topological and supramolecular.
The molecular level of the structure reflects the chemical architecture of polymer, the
stereochemical organization of the chain, the character of the attachment of links one to another. All parameters characterizing the molecular level of the structural organization can
be unambiguously related to the conditions of synthesis. The topological structure of polymer describes the organization and structure of the chain as a whole. The supramolecular
level of organization of the polymer system reflects the character of intermolecular interaction of macromolecules and the extent of order in their mutual arrangement.
It is established at present that all polymers both amorphous and crystalline possess
an extent of order determined both by the molecular structure of polymer and the methods
of its production and reprocessing.
Studies of epoxy coatings have shown that the structure is formed already in initial oligomer in the process of their synthesis. Similar data have been obtained by Catrell. He has
found that the structure emerges prior to the time of the loss of fluidity and is then fixed in
the process of hardening owing to a sharp decrease of mobility of the structural elements.
Studies of the formation specifics of coatings based on oligomers, solutions and dispersions of polymers have shown that the mechanism of this process is related to the transition of the system to a gelated state owing to the formation of local physical or chemical
bonds between structural elements and the inhibition of relaxation processes leading to the
emergence of internal stresses. Herewith, a view has been put forward and experimentally
substantiated that the formation process of epoxy coatings consists of two stages:
formation of local bonds within the limits of a small number of macromolecules,
which is accompanied with the formation of a supramolecular structure;
emergence of links between these structures and formation of the three-dimensional
network.

260

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At the first stage, despite a significant number of groups involved in the formation process, an induction period is observed on the kinetic curves for the change of the physicomechanical properties of coatings; the induction period is characterized by low physicomechanical properties and internal stresses in coatings. At the second stage, a sharp slowdown of the relaxation process and the emergence of internal stresses are observed. This
character of structural transformations is common for network polymers and is found in
studies of the hardening of coatings based on oligoester urethanes, epoxides, phenol formaldehyde, organosilicon and other polymers.
By the method of NMR, it has been shown that, depending on the chemical composition of oligomer, folding of macromolecules into supramolecular structures can be different, which, in turn, determines the distribution (on their surface) of active groups involved
in the film formation process and in the interaction with the support. To realize the largest
number of functional groups in the formation of adhesion and cohesion bonds, it is necessary to develop in oligomer systems ordered structures of anisodiametric or clustered type
from unfolded molecules.
Electron-microscopy studies of polymers showed the morphology of sparsely crosslinked polymers to differ little from the character of structural elements for linear polymers.
The major structural elements can be all morphological types (globules, spherolites,
crystallites, fibrillae, etc.) characteristic of linear polymers.
For densely crosslinked epoxy polymers obtained from oligomers with the static distribution of the functional groups, the main structural element are globules.
Variation of the structure of the initial reagents (oligomers, hardeners, solvents),
change of the formation conditions or the effect of thermal or mechanical fields on the already formed polymer do not change the morphology of the structure of a densely
crosslinked polymer: in all case, it remains globular, only the size of globules and the density of their packing do change.
Oligomers with the regular structure of the chain form associates of anisodiametric
shape from macromolecules of unfolded conformation, as well as highly organized crystals
of various morphologies. The number and size of globules change depending on the hardening conditions.
Hardening of epoxy coatings at low temperatures is accompanied with the development of large globular formation in the structureless matrix.
The subsequent heating of coatings up to 343353 K at the second stage of hardening
leads to the emergence of small globular formations and an increase of their number. Herewith, chain and band structures are formed in epoxy coatings, which is indicative of the destruction of some bonds between structural elements and their regrouping into more
complex structural elements.
According to the data by Catrell, formation of supramolecular structures is determined
both by hardening temperature and rate. At a large rate of hardening, the size of globules
formed is 2010 6 m, whereas the slow hardening at low initial temperatures is accompanied with the formation of globules of up to 9010 6 m.

8.4

Methods of modifying the structure and properties of epoxy coatings

Coatings used for protection of metallization should have a high resistance to the action of
water in boiling. The performance properties of epoxy coatings significantly depend on the
nature and concentration of hardeners. The resistance of coatings to the action of aggressive
media is significantly affected by the ratio between the value of internal stresses and adhe-

CHAPTER 8

261

sion strength of coatings. In this connection, the issues related to the development of physicochemical way of decreasing internal stresses are of great scientific and practical
significance. One of the ways to decrease them is to develop methods of modifying compositions in the process of their synthesis. Internal stresses emerging in the formation and
performance of coatings are a measure of imperfection of their structure. In this connection,
targeted synthesis of oligomers with a regular structure of the chain or their modification
by special additives make it possible to significantly reduce internal stresses in coatings.
The effect of the structure of epoxy oligomer molecules on the protective properties
of coatings based on oligomer ED-20 was studied by using compounds of various chemical
compositions and molecular structures as hardeners. Along with polyethylene polyamine,
which makes epoxy oligomers harden as the result of copolymerization by epoxy and amino
groups by way of opening the oxide rings and substituting hydrogen atoms of hydroxyl
groups, ester acids with different chain structures were used as hardeners.
Regularities in the change of internal stresses depending on the main factors, which
determine the film formation process (formation conditions, film thickness, strength of interaction at the polymersupport interface, etc.) proved to be common for coatings based
on various oligomer systems.
The rate of increment and the value of internal stresses in the formation of epoxy coatings depend on the hardening conditions. At 20C, internal stresses rise comparatively
slowly and reach an ultimate equilibrium value in 2030 days.
As the formation temperature rises, the internal stress increment rate goes up, especially significantly in the range equal to or greater than the glass-transition temperature.
When comparing the kinetics of using the functional groups of epoxy oligomer in the
formation of coatings with the internal stress increment rate, it was found that there was no
symbasis in their increment. The rate of using the functional groups in the formation of the
three-dimensional network is much faster than the rate of increment of internal stresses.
The number of epoxy groups entering into the polymerization reaction was assessed
by IR spectroscopy from the change of intensity of the absorption bands in the region of
918 and 1247 cm 1, characteristic of epoxy groups; and 3350 cm 1, for amino groups.
The structure of epoxy coatings was studied by the method of electron microscopy by
taking carbon-platinum replicas at various stages of coating formation.
The regularities obtained suggest that at 20C more than 50% of all functional groups
enter into interaction for 57 h; in 1020 h, the polymerization process is totally complete;
herewith, 5075% of epoxy groups enter into the reaction. Internal stresses under these
conditions of hardening reach the ultimate value in 2530 days.
At 80C, the number of functional groups involved in the interaction increases up to
85%, and the polymerization process ends up in 6090 min of coating formation. Internal
stresses under these formation conditions reach an ultimate value in 1012 hours of hardening.
Despite the small value of shrinkage of epoxy coatings in hardening (not more than
12%), they feature significant internal stresses up to 1015 MPa which at a film thickness of 300400 m induce a spontaneous peeling and cracking of coatings.
Internal stresses were decreased by changing the nature of hardener for epoxy systems.
The dependence of internal stresses and other mechanical properties of films on the
amount of hardener in the composition is nonmonotonous and exhibits a maximum corresponding to the formation of the largest number of crosslinks, therefore the decrease of internal stresses by changing the amount of hardener is accompanied with the worsening of
the other mechanical properties.

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14.0
1

12.0

b10, MPa

10.0

2
3

8.0

6.0
4
4.0

2.0

400

800

1200

h, m

Figure 8.1 Dependence of internal stresses on the thickness of coatings from composite epoxides
hardened by polyethylene polyamine (1), glycerol trisuccinate (2), glycerol triadipinate (4) at 120C,
as well as glycerol tricebacinate at 200C (3).

To improve the mechanical properties of coatings, use was made of ester acids with
different chain structures as a hardener. The properties of coatings from epoxy oligomer
ED-20 changed depending on the nature of trifunctional ester acid. As the length of ester
acid branchings increased, the elasticity of coatings increased too.
Coatings were formed from 6085% alcohol-acetone solutions of epoxy oligomer
and, respectively, 70% acetone solutions of glycerol trisuccinate, triadipinate and tricebacinate at a ratio 1:1. Coatings were hardened at 120C. If coatings based on glycerol tricebacinate were hardened not at 120C but at 200C, their elasticity was smaller than for films
based on triadipinate formed at 120C. This is due to the fact that at this temperature, along
with the reaction between carboxyl groups and epoxy groups, there is probably a side reaction of carboxyl and hydroxyl groups, which, in turn, leads to an additional crosslinking.
From the data on the kinetics of increment and relaxation of internal stresses, the
changes of hardness in the formation of coatings from these compositions at 120C and subsequent operation of coatings at 20C, it follows that compositions based on glycerol trisuccinate and triadipinate harden well under these conditions, and compositions with glycerol
tricebacinate harden very slowly, so that the formation of coatings from them can be performed only at 200C.
The largest internal stresses emerge in coatings hardened by glycerol trisuccinate.
These data indicate that, as the length of branchings in ester acids, which harden the epoxy
oligomer, increases, internal stresses decrease, and elasticity of coatings goes up. If the
length of branchings is higher than the optimal value, which takes place in the introduction
of glycerol tricebacinate, the hardening of the composition at 120C is not observed. With

CHAPTER 8

b, MPa
6.0

263

5.0
4.0
3.0

2.0

1.0

10

, h

12

Figure 8.2 Kinetics of increment of internal stresses in the formation of epoxy coatings with glycerol trisuccinate (1), glycerol triadipinate (2) at 120C, with glycerol tricebacinate (3) at 200C.
E .10, MPa

0.5

1.0

3
4
1

0.4

0.8

0.3

0.6

0.2

0.4

0.1

0.2

Hardness, arb. u.

1.2

5
2

10

15

20

25

30 , h

Figure 8.3 Kinetics of increment of the elasticity modulus (13), hardness (46) in the formation
of epoxy coatings with glycerol trisuccinate (14) and glycerol triadipinate (25) at 120C, with
glycerol tricebacinate (36) at 200C, amounts of E in GPa.

the formation temperature increasing up to 200C, coatings based on this composition reveal the highest physicomechanical properties.
Coatings from a composition with a hardener based on glycerol trisuccinate and triadipinate under conditions of hardening at 200C spontaneously break down due to their
high embrittlement. Figure 8.1 presents a dependence of internal stresses for coatings of different chemical compositions on the thickness of the film. It is seen in the figure that coatings based on glycerol trisuccinate and triadipinate (hardened under optimal conditions),
are characterized by a high adhesion strength within a wide range of film thicknesses.
Figures 8.2 and 8.3 present the kinetics of internal stresses, elasticity modulus and

264

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

hardness in the formation of coatings based on epoxy copolymers with various hardeners.
It is seen that the formation of coatings at 120C ends up practically in 56 h, when the
physicomechanical characteristics reach their ultimate maximal value.
Table 8.2 presents the data on the effect of the nature of hardener on the maximal internal stresses, elasticity modulus, tensile strength and adhesion strength of coatings.
Table 8.2
Hardener

b, MPa

E, MPa

p, MPa

A, MPa

6.0
1.5
2.5

0.9
0.4
1.2

15.0
5.0
35.0

13.0
10.0
15.0

Glycerol trisuccinate
Glycerol triadipinate
Glycerol tricebacinate

A specific feature of coatings based on glycerol tricebacinate is that at a high adhesion


strength, hardness, tensile strength they reveal comparatively small internal stresses.

8.5

Protective coatings from copolymers of regular structure

To improve the performance properties of coatings to decrease internal stresses in them


at a simultaneous improvement of the other physicomechanical characteristics (adhesion,
strength) techniques have been developed to produce regular-structure epoxy copolymers.
The effect of the structure of macromolecules on the structure and properties of coatings from polyester-epoxy and silicon-containing polyester-epoxy polymers of irregular
(III) and regular (I, II) structure has been studied.
Polyester-epoxy oligomers were synthesized according to the following scheme:
O
O
C[CH2OC(CH2)nCOOH]4 + 2CH2 CHCH2ORCH CH2
C CH2OC(CH2 )nCOCH2CHCH2OROCH2CHCH2OC(CH2)nCOCH2
O

OH

OH

As the diglycidyl component, use was made of hydroquinone diglycidyl and diphenylol propane diglycidyl. Organosilicon polyester amidoepoxy polymers of regular structure
were produced in two stages. At the first stage, pentaerythrite tetraadipinate was condensed
with bis-(phenyl aminomethyl)tetramethyl disiloxane:
[CH2OC(CH2)4COOH]4 + 2HNCH2Si(CH3)2OSi(CH3)2CH2N

CH2OC(CH2)4C N CH2Si(CH3)2CH2N
O

H2O

C(CH2)4COCH2 C
O

The produced copolymers, which contained phenylamino methyl xylyl and carboxyl
groups, were converted to copolymers with the regular distribution of carbon atoms in the
network by the interaction with diglycidyl esters.

CHAPTER 8

130

265

b10, MPa

100
80

60
40

3
4

20

12

18

24

30

36 , h

Figure 8.4 Kinetics of internal stresses in the formation of coatings at 160C from copolymers I (2),
II (3), III (4) and epoxy oligomer (1).

We investigated the performance properties of coatings based on copolymers of the


following chemical composition:
O
C

OH

CH3

CH2OC(CH2)4COCH2CHCH2O

C
CH3

OH
OCH2C

CH3 CH3

CHCCH2OC(CH2)4COCH2C

CH2 OC(CH2)4CNCH2SiOSi
CH3 CH3

CH2NCH2CHCH2OROCH2CHCH2C(CH2)4OCH2C
OH

OH

Copolymer III represented a product obtained by the condensation of pentaerythrite


with adipic acid and diglycidyl ester of diphenylol propane at a simultaneous charging of
the components, and was distinguished by an irregularity of the structure.
To elucidate the effect of the composition and structure of polymers on the properties
of coatings, the kinetics of increment of internal stresses and other characteristics in the
hardening of compositions was studied.
From these data, it follows that the ordering of the structure of regular-structure oligomers contributes to a 23-fold decrease of internal stresses in the formation of coatings as
the result of relaxation processes prior to the formation of adhesion bonds in the formation
of coatings. Coatings from regular-structure copolymers are also distinguished by the stability of the properties (Figs. 8.4 and 8.5).

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Hardness, arb. u.

E .104, MPa
0.6

24

0.4

16

0.2

5
6

10

15

20

2
3

25

, h

Figure 8.5 Change of the elasticity modulus (1 3) and hardness (4 6) in the formation of coatings
from copolymers I (1, 4), II (2), III (3, 6) at 160C.

From the analysis of the results on the kinetics of increment of the elasticity modulus
of these same films in the formation of coatings, it follows that the elasticity modulus reaches an ultimate value in 1015 hour of formation.
Films from copolymer II harden the most rapidly at 160C. The character of the dependence of internal stresses on the thickness of films for coatings from compositions of
various chemical compositions is linear.
Along with small internal stresses, coatings from regular-structure copolymers are
characterized by a high adhesion strength. From the comparison of the properties of coatings obtained from various copolymers based on oligomer ED-20, it follows that internal
stresses in coatings from compositions 1 and 2 are 4 to 10 times less than in coatings from
the initial epoxy oligomer hardened with polyethylene polyamine. Herewith, coatings
based on ED-20 peel off at a comparatively small thickness of 400 m. Films based on copolymers peel off at the same value of internal stresses at a thickness larger than 2500 m.
This is indicative of a much larger adhesion strength of coatings from copolymers as compared with coatings from the initial epoxy oligomer.
Table 8.3 presents the data on the physicomechanical characteristics of coatings from
regular-structure copolymers.
Table 8.3 Effect of chemical composition on the physicomechanical properties of coatings.
Film-forming
component
Copolymer I
Copolymer II
Copolymer III
ED-20

p, MPa

E, GPa

b, MPa

A, MPa

Margin of cohesion
strength

25.2
34.3
21.5
60.0

1.5
2.4
1.2
2.4

1.4
0.7
2.2
7.0

150
150

130

18
49
9
8

The tensile strength of films from regular-structure copolymers is 2050% larger than
for irregular-structure films, but 1.52 times smaller than the strength of films from ED-20.
However, in view of the small magnitude of internal stresses for coatings from regular-structure copolymers, their cohesion strength is 26 times higher than that of films from
oligomer ED-20. As the result, coatings from regular-structure copolymers are more durable than coatings from ED-20.

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267

Based on the regularities obtained, a composition based on epoxy oligomer ED-20 was
developed and a hardener with the regular structure of molecules; the composition hardens
for several minutes to form coatings with a high adhesion strength to metallized combined
materials from polypropylene and lavsan.

8.6

Combined metallized materials for dairy produce packing

8.6.1 Combined material based on polyethylene, paper and aluminium foil


Combined material consists of five layers, each of which has its own functionality:
the first (outer) layer from polyethylene; it is intended for protection of the paper base
from moisture and contamination;
the second layer from base paper of pure cellulose; density, 200250 g/m2. This layer is the load-bearing structure of a packaging to provide its good rigidity and to give it a
geometrically constant shape. These characteristics are obtained owing to long fibres, from
which paper consists. Besides, paper is a protective layer;
the third layer from polyethylene; it serves for glueing the paper base and aluminium
foil;
the fourth layer from aluminium foil 9 m thick. It is the most essential barrier for
the action of atmospheric agents and gases. Even at this thickness, there are almost no
microholes on the surface of foil. This layer also protects well the contents of a packaging
from the light, thus preserving for a long time the primary organoleptic characteristics of
products. Besides, the plasticity of this layer makes it possible to bend the edges of a package and its angles without flaws. This layer is required for induction heat sealing;
the fifth (internal) layer from polyethylene. Its thickness is much larger than that of
the first and third layers. It consists of two sublayers: the adhesion oxidized sublayer and
the unoxidized sublayer, which is in contact with the product. The main aim of this layer is
to enhance the protective barrier and to facilitate the sealing (longitudinal and two transverse ones).
Fabrication of a five-layer combined material includes the following operations: unwinding of the base paper, gas-flame treatment of the base paper, coating of the external
side of the paper with decorative printing and a layer of polyethylene, corona treatment of
aluminium band, application of the intermediate polyethylene layer between aluminium foil
and base paper, application of the bilayer inner coating from the melt of polyethylene on
the side of aluminium foil, cutting of edges, winding of ready material to rolls.
When elaborating the process regimes for production of combined material, the main
parameters of the lamination process were varied: temperature by the extruders zones,
working speed of the base sheet, temperature of cooling water at the input to the pressure
rollers of the laminators, frequency of rotation of augers at the startup, melting temperature
of polyethylene in the flat-die drawhole of the extruders, pressure of the melt of polyethylene before the package of the filtering meshes, working pressure of gas and air fed to the
burners of the gas-flame station, unit force of the laminators at the winding and unwinding
units, parameters of corona treatment of the surface of the base.
The parameters of the process were chosen such that to provide for good adhesion of
all five layers of combined material, to achieve the required mass of the polyethylene coating in an area of 1 m2 at a high rate of the process, to exclude the oxidation of the inner
polyethylene coating in contact with the product.

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

The following regime of the technological process for fabrication of combined material was established and used in production of pilot batches at the Enterprise for Production
of Packagings and Containers of the Kuban Agroindustrial Complex:
the temperature of the polyethylene melt applied to the base paper and foil is within
305312C for the external coating; 305318C, for the intermediate layer; 303324C,
for the oxidized layer; and 275281C, for the unoxidized layer of the internal coating;
the speed of travel of the base sheet, 10010 m/min;
the number of blocks on the corona discharge units, 4345;
the ratio of air and gas pressure in the installation, 37%;
the temperature of cooling water at the output to the pressure rolls of the laminators,
22C.
Good quality of the combined material is one of the essential conditions for the stable
operation of automatic filling machines at dairy plants. It provides for minimal losses of
packaged dairy produce in its transportation, storage and sales. Therefore, the correct choice
of the main parameters for the output control at the combined-material manufacturing
plants and the input control at the dairy enterprises is one of the major issues in the
producerconsumer chain.
When phasing in to the optimal regime of production, making it possible to produce
combined material of required quality, specimens from 22 pilot batches were chosen and
their physicomechanical tests carried out. The following parameters were taken into account: the mass of 1 m2 of polyethylene coatings (layer-by-layer), the thickness of combined material, adhesion of the polyethylene layers to the paper base, resistance to peeling
(aluminium foilpolyethylene).
Control of the mass of 1 m2 polyethylene coatings and bonding layer is required for
the correct monitoring of the production of combined packaging material based on paper
(paperboard) and aluminium foil and is of great significance for production of packaging
material of required quality.
A method of determining the mass of a 1 m2 polyethylene layer in the combined material based on paper and aluminium foil has been developed; the method was submitted as
the application for an invention and became the basis of a new methodology of determining
the mass of the polyethylene layer.
Simultaneously with the physicomechanical tests, the sanitary and chemical assessment of pilot batches of combined material was carried out in accordance with the Instruction and Recommendations of the Ministry of Health. Distilled water and a 0.3% solution
of lactic acid were used as model media. Extracts for studies were obtained under conditions
close to the operational conditions of packaging material. Model media were poured into
packs from the investigated material of 1 litre capacity. Upon filling, packs were hermetically sealed on a laboratory sealing machine at the regimes similar to the conditions of sealing in commercial automatic machines. Extracts were kept for 1 and 3 days at room
temperature. The organoleptic assessment of aqueous extracts was carried out by the method of extended triangle by the five-point scale at room and elevated temperatures
(4060C).
Sanitary and chemical investigations of test specimens of the material were also carried out with the aim to determine the extent of migration in extracts of low-molecular-mass
substances. The oxidizability of aqueous extracts was determined by the dichromate method. The content of brominated substances in aqueous extracts and lactic extracts was found
by the method of volumetric iodometry. The content of formaldehyde was assessed by the
method of thin-layer chromatography.

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269

The results of the studies have shown that in specimens of the final test batches of combined material the total migration of low-molecular-mass substances is insignificant; the
presence of formaldehyde was not found. The regimes at which the final batches were produced, satisfying the requirements of dairy industry by the sanitarychemical and performance properties, have been entered into the technical documents for the production of
combined material.
Thus, the effect of the process parameters on the quality parameters of combined material has been studied; the method of determining the mass of 1 m2 of the polyethylene layer has been determined; the nominal values of the parameters and tolerances for them have
been found; sanitary-chemical studies of the test specimens of combined material have been
carried out; the technological regulations for the production of combined material has been
developed; the technical specifications for a combined material based on paper and aluminium foil for packaging milk and dairy products have been developed and approved.
8.6.2 Hermeticity of polymer packaging
One of the main conditions for preserving the quality of a packaged product and preventing
its losses is the air-tightness of the packaging, which should not be disturbed on the way of
the product from producer to consumer.
At present, the air-tightness of various kinds of consumer containers from polymer materials in dairy industry enterprises is controlled visually. This control fails to provide an
objective assessment of quality and leads to losses of milk and dairy products during the
storage, transportation and sales.
Based on the literary and patent data in the field of nondestructive methods of control,
it is proposed to use the filled-system and optical methods of leakage detection for the assessment of the air-tightness of consumer containers used for packaging milk and dairy
products. These methods are informative, do not require complex equipment, are simple
and provide express information.
Two instrumental methods of operational air-tightness control have been developed:
the method of determining the air-tightness of consumer containers capped with foil with a
thermolacquer coating (the method of TL measurements) and the method of determining
the air-tightness of polyethylene packets of the type of Elecster and Finnpack using a photoelectric colorimeter (the method of PC measurements).
The essence of the TL method is to create a certain vacuum in a hermetically sealed
chamber with a capped (unfilled) consumer container. Due to the pressure difference inside
and outside the tested package, its shape and size change (it swells). If the package is
air-tight, after the removal of vacuum it acquires its initial shape. If the air-tightness of the
package is disturbed, no change of size is observed under the action of vacuum. When the
integrity of the package is violated during its exposure to vacuum, the leakage is determined
visually (breakdown, peeling and other defects) or (if there are microdefects) the package
is compressed after the vacuum is removed.
Tests of the consumer containers capped with foil with a thermolacquer coating were
carried out in a vacuum exciccator and in a vacuum cabinet at a maximum vacuum of 0.09
MPa. To determine the optimal conditions required for the assessment of the air-tightness
of consumer containers of 250 g capacity, the value of vacuum was varied within the range
of 0.0650.015 MPa, exposure time was from 1 up 10 min (Table 8.6.1). The result of the
experiment was taken to be the share of packages with violated air-tightness in percent.
At a vacuum of 0.0630.065 MPa, practically 100% of the specimens break down.

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

The vacuum of 0.0630.065 MPa for this type of packagings is critical and can be used as
a characteristic of strength of sealed thermoformed containers. It should be noted that the
parameter depends on the kind and quality of raw materials used to produce polymer sheet
materials (granulated polymer), on the geometric size and shape of the package, on the correct observance of the process regime of the fabrication of consumer containers.
Table 8.6.1 Data on the air-tightness of polystyrene containers.
Vacuum, MPa

Non-airtightness, in %, at exposure time (in min)

0.065
0.063
0.060
0.055
0.050
0.040
0.030
0.025
0.020
0.015

10

100
100
81.25

25
37.5
20.5
6.25
0
0

75

18.75
6.25
12.5
18.75
12.5
6.25

37.5
25
12.5
18.75
6.25
6.25
12.5

94

68.75
37.5
50
12.5
12.5
12.5

43.75
31.25

18.75
12.5
12.5

Note: The result was taken to be the mean arithmetic test of 16 specimens.

Analysis of the dependence of the share of non-air-tight containers on the value of vacuum at different exposures (Fig. 8.6.1) and that of the share of non-air-tight containers on
the exposure time at fixed values of vacuum (Fig. 8.6.2) made it possible to find the optimal
exposure time of specimens to be 5 min and the value of vacuum, 0.0150.04 MPa.
N, %
100
1

80

60

40
3

20

5
7

10 , min

Figure 8.6.1 Dependence of the share of unsealed containers (N) on exposure time. Residual pressure, MPa: 1, 0.06; 2, 0.05; 3, 0.04; 4, 0.03; 5, 0.025; 6, 0.02; 7, 0.015.

CHAPTER 8

271

N, %
100

80

60

40
3

20

1
4

0
0.01

0.02

0.03

0.04

0.05

P, MPa

Figure 8.6.2 Dependence of the share of unsealed containers (N) on pressure. Exposure time, min:
1, 10; 2, 5; 3, 3, 4, 1.

The final conclusion on the optimal characteristics was made based on the determination of the maximal load acting on a package in transportation, storage and sales.
To monitor the air-tightness of Elecster- and Finnpack-type packages, it was proposed
to test the optical method of nondestructive control. The method is based on the determination of traces of milk in water by the results of optical-density changes of water, in which
packs with milk were kept under a load. This approach makes it possible to reveal the presence of microdefects in milk packages in the case when it does not appear possible to assess
the absence of air-tightness visually. To reveal the presence of milk in water, use was made
of refractometers of RPL-3 and IRP-4 type (measurement of the refractive index), and also
a FEK-M photocolorimeter (measurement of optical density).
It has been found that the refractometric method can not be used for these purposes,
because the experimental data are within the error of the experiment.
Positive results were obtained using a FEK-M photocolorimeter. The maximal sensitivity of the instrument in this range of concentrations is observed when using cuvettes with
the working length of 3 cm and a yellow light filter.
The elaboration of the proposed method of monitoring the air-tightness was carried out
on 500-ml Elecster packages filled with milk; the packages were fabricated from imported
black-and-white bilayer coextruded polyethylene film. A washed and dried package with
milk was placed into a bath, into which 1 litre of water was poured; after that a load was
applied to the package, under which the specimen package was held for a certain time. Then
the package was removed from the bath, a sample of water was taken and its optical density
was determined on an FEK-M. It proved that for determining the optimal conditions of using the leakage-search method developed it is expedient to use packages with microdefects.
To determine under optimal condition the air-tightness of Elecster-type packages of 500
cm3 capacity, the load was varied within the range of 30 up to 70 N; exposure time, from
0.5 up to 2 min (Table 8.6.2).

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POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Table 8.6.2 Results of the air-tightness control of Elecster-type packs (with microdefects).
Load, N

Exposure time, min

Optimal density

Content of milk in water, %

30
30
30
50
50
70
70
70

0.5
1
2
0.5
1
0.5
1
2

0.02
0.087
0.02
0.03
0.089
0.11
0.11
0.11

0.003
0.014
0.003
0.006
0.015
0.02
0.02
0.02

Note: In all cases the solution was clear.

Analysis of the experimental data and their recalculation for an additional load emerging in transportation, would enable making the optimal conditions of monitoring the
air-tightness of polyethylene milk packages of the type of Elecster and Finnpack more concrete.
These parameters were used to develop the protocol for determining the air-tightness
of polyethylene bags of the type of Elecster and Finnpack using a photoelectric colorimeter.
The developed methods of monitoring the air-tightness passed the metrological certification and were assigned the state register numbers.
The methods considered were included in The Book of Methods of Input and Production Control of Packaging Materials and Consumer Containers developed by the Laboratory of Packaging, All-Russian Research Institute of Dairy Industry (VNIKMI).
8.6.3 Coextruded polyethylene films for packaging dairy produce and
their quality indices
A widespread method of packaging milk at present is using disposable containers, which
became an integral part of the production process. The development and improvement of
the kinds of packaging is aimed mainly to preserve the quality and nutritive value of the
product.
The modern milk packaging should satisfy a whole range of requirements: it should
be harmless for man; to protect milk from spoilage, contamination and the effect of external
factors, such as moisture and foreign smells; to provide for the preservation of the product
in transportation and storage; to have a small mass and area; to have an attractive appearance; to be cheap and easy to handle.
One of the widespread methods of packaging milk is its production in soft polyethylene packs. Polyethylene film as a packaging material conforms to all the above requirements. Such of its properties as nontoxicity, strength, elasticity; vapour, water and gas
impermeability; chemical inertness, relative simplicity of the production process stipulated
the wide use of this material in dairy industry. Besides, polyethylene film is the cheapest as
compared with other packaging materials.
In this country, packaging of milk and dairy products is performed using filled polyethylene film produced by coextrusion from low-density polyethylene (LDPE), mainly of
grade 17504-006, with addition of 3% titanium dioxide and 0.08% slip additive Armide O.

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273

Titanium dioxide used as a filler is imported. In this connection, an important task is modification of coextruded films with the view to exclude or reduce the content of titanium dioxide.
The possibility of increasing the volume of production of this film and its modification
with the view of expanding the range of packaging materials has been studied.
Analysis of the home raw-material base and process equipment for production of films
made it possible to pinpoint the real directions of modification. Reduction of the consumption of materials in production of the film without deteriorating its properties is possible owing to the use of the features of the coextrusion method of production. The bilayer
polyethylene film produced by the extrusion method has no drawbacks characteristic of individual films; the use of this method reduces the probability of random defects. Also, it
makes possible the protection from the light due to the introduction of pigment into the outer
layer of the film.
Considering the above-said, and also based on the analysis of the existing range of
grades of LDPE compositions permitted for use by the Ministry of Health, new constructions of films have been proposed.
Test batches of films were produced at the Borisov Plant Polimiz on the Finnpack
equipment of the firm Tuomo Halonen (Finland) and Rotex 40 D (Germany). Four types of
coextrusion polyethylene film were produced (2, transparent; 2, semitransparent); LDPE
(base grade 17504006) and its compositions for them were fabricated by the Novopolotsk
Industrial Association Polimir (see Table 8.6.3).
Table 8.6.3 LDPE compositions for manufacturing coextrusion films.
LDPE grade

Content, %
titanium dioxide

Armide O

3.0

0.08
0.08

17504006
175132
175225

Regimes for the production of the films were identical for all their types (Table 8.6.4).
The types of the films are given in Table 8.6.5.
Table 8.6.4 Regimes of production of coextruded polyethylene films.
Specimen no

1
2
3
4

Equipment

Finnpack
Rotex 40D
Finnpack
Finnpack

Temperature at exit
Auger
from auger head, C rotation frequency,
rpm
190
190
190
190200

6010
400500
6010
6070

Extrusion rate,
m/min
282
2226
282
2530

It is known that the possibility of phasing in novel packaging materials intended for
contact with food products depends on a range of conditions. They include the results of
studies of the quality of films with the aim to assess their effect on the human organism, the
determination of the physicomechanical characteristi