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Printing on Polymers: Fundamentals and Applications

Printing on Polymers: Fundamentals and Applications

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Printing on Polymers: Fundamentals and Applications

4.5/5 (3 évaluations)
1,208 pages
353 heures
Sep 24, 2015


Printing on Polymers: Fundamentals and Applications is the first authoritative reference covering the most important developments in the field of printing on polymers, their composites, nanocomposites, and gels.

The book examines the current state-of-the-art and new challenges in the formulation of inks, surface activation of polymer surfaces, and various methods of printing. The book equips engineers and materials scientists with the tools required to select the correct method, assess the quality of the result, reduce costs, and keep up-to-date with regulations and environmental concerns.

Choosing the correct way of decorating a particular polymer is an important part of the production process. Although printing on polymeric substrates can have desired positive effects, there can be problems associated with various decorating techniques. Physical, chemical, and thermal interactions can cause problems, such as cracking, peeling, or dulling. Safety, environmental sustainability, and cost are also significant factors which need to be considered.

With contributions from leading researchers from industry, academia, and private research institutions, this book serves as a one-stop reference for this field—from print ink manufacture to polymer surface modification and characterization; and from printing methods to applications and end-of-life issues.

  • Enables engineers to select the correct decoration method for each material and application, assess print quality, and reduce costs
  • Increases familiarity with the terminology, tests, processes, techniques, and regulations of printing on plastic, which reduces the risk of adverse reactions, such as cracking, peeling, or dulling of the print
  • Addresses the issues of environmental impact and cost when printing on polymeric substrates
  • Features contributions from leading researchers from industry, academia, and private research institutions
Sep 24, 2015

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Printing on Polymers - Elsevier Science

Printing on Polymers

Fundamentals and Applications

Joanna Izdebska

Sabu Thomas

Table of Contents

Cover image

Title page

Series Page




1. Printing on Polymers: Theory and Practice

1.1. Introduction—The Impact of Printing

1.2. Printing Techniques

1.3. Printing Bases

1.4. Printability

1.5. Surface Wettability

1.6. Print Quality

1.7. Plastic Printing Industry

2. Polymeric Materials—Structure, Properties, and Applications

2.1. Introduction

2.2. Structure of a Polymer

2.3. Properties of Polymers

2.4. Application of Polymers

2.5. Conclusion

3. Printing Ink Formulations

3.1. Introduction

3.2. Individual Ink Components

3.3. Inks Manufacture

3.4. Selected Inks for Individual Printing Processes

3.5. Functional Inks

3.6. Summary

4. Additives for Ink Manufacture

4.1. Definition of an Additive

4.2. Surfactants: Wetting and Dispersing Agents

4.3. Adhesion Promoters

4.4. Waxes

4.5. Driers

4.6. Rheology Modifier

4.7. Other Additives

4.8. Additives for Radiation-Curing Inks

4.9. Performance Additives

5. Advanced Nanoscale Materials for Ink Manufacture

5.1. Introduction

5.2. Nanoscale Materials for Ink Manufacture

5.3. Conclusions and Outlook

6. Rheology of Printing Inks

6.1. Newtonian and Non-Newtonian Fluids

7. Low-Pressure Plasma-Assisted Polymer Surface Modifications

7.1. Low-Pressure Oxygen Plasma

7.2. Reactive Plasma Species and their Interaction with Polymers for Printing

7.3. Flowing Afterglow

7.4. Peculiarities of Particular Polymers

7.5. Etching, Nanostructuring, and Wettability

7.6. Concluding Remarks

8. Corona Treatment

8.1. Corona Discharge Treatment: Introduction

8.2. Surface Changes, Film Wettability, and Printability

8.3. Peculiarities of Particular Polymers

8.4. Aging Process of Corona-Treated Films

8.5. Concluding Remarks

9. Polymer Surface Modifications by Coating

9.1. Organic Modifications of Polymer Surface

9.2. Inorganic Coating

9.3. Metallurgical Coating

10. Other Methods of Polymer Surface Modifications

10.1. Introduction

10.2. Laser Beam Processing for Polymer Surface Modifications

10.3. Micromachining

10.4. Other Energy Beam Processing Techniques

11. Flexographic Printing

11.1. Fundamentals of Flexographic Printing

11.2. Production Materials

11.3. Flexographic Printing Benefits

11.4. Flexographic Market and its Future

12. Gravure Printing

12.1. Market of Gravure Printing

12.2. Printing Process

12.3. Gravure Printing Inks

12.4. Gravure Cylinder Manufacturing

12.5. Structure of Gravure Printing Presses

12.6. Applications and Further Developments

13. Offset Printing

13.1. Fundamentals of Offset Printing

13.2. Offset Inks

13.3. Construction of Printing Presses for Offset Printing

13.4. Print Quality Control in Waterless Offset on Polymer Materials

14. Inkjet Printing

14.1. Fundamentals of Inkjet Printing Technology

14.2. Physical and Chemical Properties of Inkjet Printing Inks

14.3. Droplet Ink Behavior on the Substrate

14.4. Polymer in Inkjet Ink Formulation

14.5. Polymers as Inkjet Printing Substrate

14.6. Future in Inkjet Printing

15. Screen Printing

15.1. Fundamentals of Screen Printing

15.2. Stencil/Plate Making

15.3. Imaging, Hand-Cut Stencils, Photostencils, Computer to Screen Systems

15.4. Printing Process

15.5. Screen Printing Industry

16. Pad Printing

16.1. History

16.2. Basics of Pad Printing

16.3. Basic Elements of Pad Printing

16.4. Application of the Pad Printing

17. Embossing Process

17.1. Fundamentals of Embossing

17.2. Hot Embossing Modes

17.3. Influence of Polymer Performance on Embossing Features

17.4. Application Example: R2R Hot Embossing Holographic Images on BOPP Shrink Film

17.5. Outlook

18. 3-D Printing

18.1. Introduction

18.2. Fundamentals of 3-D Printing

18.3. Applications

18.4. 3-D-Printing Process

18.5. 3-D Printable Materials

18.5. Electrically Conductive Polymers

18.6. 3-D Bioprinting

18.7. Conclusions

19. Theory, Modeling, and Simulation of Printing

19.1. Introduction

19.2. Measuring and Modeling Reflection Properties for Color Prediction

19.3. Light Scattering and Absorption

19.4. Spectral Reflectance Prediction Models for Colored Halftones

19.5. Multilayer Constructions

19.6. Surface and Interface Reflections

19.7. Transparent and Translucent Substrates

19.8. Conclusions

20. Characterization of Print Quality in Terms of Colorimetric Aspects

20.1. Colorimetric Aspects

20.2. Characterization of Print Quality

21. Characterization of Mechanical Properties of Prints

21.1. Introduction

21.2. Ink Abrasion Resistance of Polymer Substrates

21.3. Scratch Resistance of Polymer Substrates

21.4. Summary

22. Aging and Degradation of Printed Materials

22.1. Aging and Degradation: Definitions

22.2. Models of Artificial Aging

22.3. Degradation of Polymer Materials

22.4. Methods of Testing the Aging Process and Degradation

22.5. Polymeric Substrate Degradation

22.6. Impact of Radiation Artificial Aging on Print

22.7. Summary

23. Applications of Printed Materials

23.1. Introduction

23.2. Packaging

23.3. Labels

23.4. Printed Electronics

23.5. Household Equipment

23.6. Promotional Gifts and Materials

23.7. Others

24. Microcapsules in Printing

24.1. Introduction

24.2. Microcapsules and Microspheres

24.3. Types of Release Mechanism

24.4. Microencapsulation

24.5. Application of Microcapsules in Graphic and Paper Industry

25. Environmental and Safety Issues of Polymers and Polymeric Material in the Printing Industry

25.1. Introduction

25.2. Sustainable Development

25.3. Life-Cycle Assessment

25.4. LCA and Toxic Risk Assessment

25.5. Printing Industry and Sustainability

25.6. Assessment of Polymers and Polymeric Materials

25.7. Summary


Series Page



Series Editor: Sina Ebnesajjad, PhD (sina@FluoroConsultants.com)

President, FluoroConsultants Group, LLC

Chadds Ford, PA, USA


The PDL Handbook Series is aimed at a wide range of engineers and other professionals working in the plastics industry, and related sectors using plastics and adhesives.

PDL is a series of data books, reference works and practical guides covering plastics engineering, applications, processing, and manufacturing, and applied aspects of polymer science, elastomers and adhesives.

Recent titles in the series

Biopolymers: Processing and Products, Michael Niaounakis (ISBN: 9780323266987)

Biopolymers: Reuse, Recycling, and Disposal, Michael Niaounakis (ISBN: 9781455731459)

Carbon Nanotube Reinforced Composites, Marcio Loos (ISBN: 9781455731954)

Extrusion, 2e, John Wagner & Eldridge Mount (ISBN: 9781437734812)

Fluoroplastics, Volume 1, 2e, Sina Ebnesajjad (ISBN: 9781455731992)

Handbook of Biopolymers and Biodegradable Plastics, Sina Ebnesajjad (ISBN: 9781455728343)

Handbook of Molded Part Shrinkage and Warpage, Jerry Fischer (ISBN: 9781455725977)

Handbook of Polymer Applications in Medicine and Medical Devices, Kayvon Modjarrad & Sina Ebnesajjad (ISBN: 9780323228053)

Handbook of Thermoplastic Elastomers, Jiri G Drobny (ISBN: 9780323221368)

Handbook of Thermoset Plastics, 2e, Hanna Dodiuk & Sidney Goodman (ISBN: 9781455731077)

High Performance Polymers, 2e, Johannes Karl Fink (ISBN: 9780323312226)

Introduction to Fluoropolymers, Sina Ebnesajjad (ISBN: 9781455774425)

Ionizing Radiation and Polymers, Jiri G Drobny (ISBN: 9781455778812)

Manufacturing Flexible Packaging, Thomas Dunn (ISBN: 9780323264365)

Plastic Films in Food Packaging, Sina Ebnesajjad (ISBN: 9781455731121)

Plastics in Medical Devices, 2e, Vinny Sastri (ISBN: 9781455732012)

Polylactic Acid, Rahmat et al. (ISBN: 9781437744590)

Polyvinyl Fluoride, Sina Ebnesajjad (ISBN: 9781455778850)

Reactive Polymers, 2e, Johannes Karl Fink (ISBN: 9781455731497)

The Effect of Creep and Other Time Related Factors on Plastics and Elastomers, 3e, Laurence McKeen (ISBN: 9780323353137)

The Effect of Long Term Thermal Exposure on Plastics and Elastomers, Laurence McKeen (ISBN: 9780323221085)

The Effect of Sterilization on Plastics and Elastomers, 3e, Laurence McKeen (ISBN: 9781455725984)

The Effect of Temperature and Other Factors on Plastics and Elastomers, 3e, Laurence McKeen (ISBN: 9780323310161)

The Effect of UV Light and Weather on Plastics and Elastomers, 3e, Laurence McKeen (ISBN: 9781455728510)

Thermoforming of Single and Multilayer Laminates, Ali Ashter (ISBN: 9781455731725)

Thermoplastics and Thermoplastic Composites, 2e, Michel Biron (ISBN: 9781455778980)

Thermosets and Composites, 2e, Michel Biron (ISBN: 9781455731244)

To submit a new book proposal for the series, or place an order, please contact David Jackson, Acquisitions Editor david.jackson@elsevier.com


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Printed and bound in the United States of America


Bin Bao,     Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Green Printing, Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China

Daniel Bohn,     Bergische Universität Wuppertal, Wuppertal, Germany

Tomislav Cigula,     Faculty of Graphic Arts, University of Zagreb, Zagreb, Croatia

Timothy C. Claypole,     College of Engineering, Swansea University, Swansea, UK

Ludovic G. Coppel,     The Norwegian Color and Visual Computing Laboratory, Gjøvik, Norway

Michael Dattner,     Innovation Management, BST eltromat International GmbH, Bielefeld, Germany

Sandra Dedijer,     Department of Graphic Engineering and Design, Faculty of Technical Sciences, University of Novi Sad, Novi Sad, Serbia

Srđan Draganov,     Department of Graphic Engineering and Design, Faculty of Technical Sciences, University of Novi Sad, Novi Sad, Serbia

Urška Stankovič Elesini,     Faculty of Natural Sciences and Engineering, University of Ljubljana, Ljubljana, Slovenia

Marta Gajadhur,     Department of Printing Technology, Institute of Mechanics and Printing, Faculty of Production Engineering, Warsaw University of Technology, Warsaw, Poland

Y.C. Guan,     Beihang University, Beijing, P.R. China

Atsushi Hotta,     Department of Mechanical Engineering, Keio University, Yokohama, Japan

Veronika Husovska,     Western Michigan University, Chemical and Paper Engineering, College of Engineering and Applied Science, Kalamazoo, USA

Joanna Izdebska,     Department of Printing Technology, Faculty of Production Engineering, Mechanics and Printing Institute,Warsaw University of Technology, Warsaw, Poland

Ivana Jurič,     Department of Graphic Engineering and Design, Faculty of Technical Sciences, University of Novi Sad, Novi Sad, Serbia

Igor Karlović,     Department of Graphic Engineering and Design, Faculty of Technical Sciences, University of Novi Sad, Novi Sad, Serbia

Nemanja Kašiković,     Department of Graphic Engineering and Design, Faculty of Technical Sciences, University of Novi Sad, Novi Sad, Serbia

Fengyu Li,     Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Green Printing, Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China

Shiwei Lin,     College of Materials and Chemical Engineering, Hainan University, Haikou, People's Republic of China

K. Liu,     Singapore Institute of Manufacturing Technology, Singapore, Singapore

Tomoki Maeda,     Department of Mechanical Engineering, Keio University, Yokohama, Japan

Miran Mozetič,     Jozef Stefan Institute, Ljubljana, Slovenia

Dragoljub Novaković,     Department of Graphic Engineering and Design, Faculty of Technical Sciences, University of Novi Sad, Novi Sad, Serbia

Magdolna Pál,     Department of Graphic Engineering and Design, Faculty of Technical Sciences, University of Novi Sad, Novi Sad, Serbia

Živko Pavlović,     Department of Graphic Engineering and Design, Faculty of Technical Sciences, University of Novi Sad, Novi Sad, Serbia

Alexandra Pekarovicova,     Western Michigan University, Chemical and Paper Engineering, College of Engineering and Applied Science, Kalamazoo, USA

C.V. Pious,     International and Interuniversity Center for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, India

Sanja Mahović Poljaček,     Faculty of Graphic Arts, University of Zagreb, Zagreb, Croatia

Kirsten Radermacher,     Department of Print and Media Technologies, University of Wuppertal, Wuppertal, Germany

Atasheh Soleimani-Gorgani,     Department of Printing Science and Technology, Institute for Color Science and Technology, Tehran, Iran

Yanlin Song,     Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Green Printing, Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China

Rozalia Szentgyörgyvölgyi,     Institute of Media Technology, Obuda University, Budapest, Hungary

Daniel J. Thomas,     College of Engineering, Swansea University, Swansea, UK

Sabu Thomas,     International and Interuniversity Center for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, India

Kazuhisa Tsuji,     Department of Mechanical Engineering, Keio University, Yokohama, Japan

Raša Urbas,     Faculty of Natural Sciences and Engineering, University of Ljubljana, Ljubljana, Slovenia

Alenka Vesel,     Jozef Stefan Institute, Ljubljana, Slovenia

Gojko Vladić,     Department of Graphic Engineering and Design, Faculty of Technical Sciences, University of Novi Sad, Novi Sad, Serbia

Z.K. Wang,     Singapore Institute of Manufacturing Technology, Singapore, Singapore

S.M. Yuan,     Beihang University, Beijing, P.R. China

H.Y. Zheng,     Singapore Institute of Manufacturing Technology, Singapore, Singapore

Zuzanna Żołek-Tryznowska,     Department of Printing Technology, Faculty of Production Engineering, Mechanics and Printing Institute, Warsaw University of Technology, Warsaw, Poland


The purpose of this book is to prepare a comprehensive, structured publication gathering together both scattered knowledge and the results of studies in the field of polymeric materials conducted in the research centers all around the world.

I met Prof. Sabu Thomas during the Third International Multicomponent Polymer Conference (Third IMPC) in India in 2012. From the beginning, we knew that the areas of our interests complement each other very well. We immediately understood each other well and felt that by combining mutual knowledge and interests we can establish a successful and long-lasting cooperation.

Last year, Prof. Sabu Thomas as a visiting professor lectured at the Warsaw University of Technology, Faculty of Engineering, where I am currently working. It was then when we have decided to coauthor a book. Professor's experience in the field of polymeric materials in combination with my knowledge in printing and inks enabled us to outline the book, which just came to your hands. With the help of our scientist friends from around the world, working in the field of printing, materials science and physical–chemical processes, we were able to prepare this publication. We would like to thank all of them for the excellent cooperation and the knowledge that they wanted to share.

There are books about printing available on the market, but ours is exceptional in a sense that it is entirely dedicated to printing on plastics, both classic and biodegradable. These materials are becoming increasingly important as printing substrates, and their application is growing in the recent years. Furthermore, polymers are replacing other materials used so far in many different areas, such as packaging, agriculture, or automotive industry. Properly selected plastics can substitute other materials such as metal, paper, and glass.

Modern printing industry is very interdisciplinary and draws knowledge from multitude of disciplines. High-quality printing requires employment of knowledge of material science, physical–chemical phenomena, printing techniques, preparation of the polymers surface before printing, and factors affecting the printing process, among others. Print quality is today a key aspect of aesthetics and marketing, testifies to the quality of the product, distinguishes it, and may decide about its attractiveness or contribute to its individual character.

Authors and editors have made every effort to create a compendium of knowledge on application of polymer materials in printing that is at the same time practical, comprehensive, exhaustive, yet remains an accessible publication. Furthermore, the aim of the book is to be the source of the current information and latest developments in the field for the moment of publication. We have designed the book so that the reader may acquire not only broad and deep knowledge, but also find fundamentals and explanations of the basic phenomena that many times are difficult to explain and often overlooked. This book should become an invaluable help not only for students and lecturers, but also for printers, manufacturers of printing materials, and other industries associated with the use of printed plastics.

Joanna Izdebska,     Warsaw, June 2015


Printing on Polymers

Theory and Practice

Joanna Izdebska     Department of Printing Technology, Faculty of Production Engineering, Mechanics and Printing Institute, Warsaw University of Technology, Warsaw, Poland


In this chapter, a short history of printing and its meaning are given. All printing techniques used for polymer printing as well as some decorative methods are briefly presented. The suitability of various printing techniques to print selected polymeric materials and packaging materials is discussed. Because substrate properties are the primary factors that determine the printability of polymers bases such as films, multilayer films, semirigid and rigid plastic sheets, molded products, synthetic papers, and polymer-coated boards are described. In the case of these nonabsorbent materials, the key factor that determines printability is their surface free energy, which has an impact on material wettability and adhesion of ink to the substrate. All these problems, as well as the most important points related to print quality, are presented in this chapter. At the end, some facts about the plastic printing industry are included.


Plastic substrates; Print quality; Printability; Printed polymers; Printing techniques; Surface-free energy; Surface wetting


1.1 Introduction—The Impact of Printing 1

1.2 Printing Techniques 2

1.2.1 Flat Printing 3

1.2.2 Relief Printing 4

1.2.3 Gravure Printing 5

1.2.4 Stencil Printing 5

1.2.5 Digital Printing 6

1.2.6 Three-Dimensional Printing 7

1.2.7 Hybrid Printing 7

1.2.8 Various Printing Techniques for Polymer Decoration 7

1.3 Printing Bases 7

1.3.1 Films 9

1.3.2 Multilayer Films 10

1.3.3 Semirigid and Rigid Plastic Sheets 10

1.3.4 Injection Molded Products 11

1.3.5 Synthetic Papers and Polymer-Coated Boards 11

1.4 Printability 11

1.5 Surface Wettability 12

1.5.1 Surface Tension of Inks 12

1.5.2 Surface Free Energy of Printing Substrates 13 Devices for Measurement of the Contact Angle 13 Measurement Liquid, Pens, etc. 14

1.6 Print Quality 15

1.6.1 Factors of Printing Processes Influencing the Print Quality 15

1.6.2 Impact of Ink and Substrate Properties on the Print Quality 15

1.6.3 Parameters Used in Quality Assessment 16

1.7 Plastic Printing Industry 17

References 18

1.1. Introduction—The Impact of Printing

The history of European printing is relatively short, as it dates back to the fifteenth century. At that time, Gutenberg began with printing using a press and movable types. However, attempts to record important information and events or attempts to decorate materials including ceramics have taken place since the dawn of the human history. Fired clay tablets or wooden stamps were used for this purpose. However, it was Gutenberg's invention that was considered the beginning of the development of printing techniques, multiple duplication of the same picture from the form on the printing substrate using ink (Gregory, 1996; Kipphan, 2001).

The first printing substrate was paper, and it is still a dominant one. However, very diverse properties of plastics led to the situation in which they started to play an important role in various areas, including as printed materials. In 1912, when cellophane film (made of regenerated cellulose) started to be produced on a mass scale, its transparency and barrier properties were first used. It was not until the 1930s that cellophane began to be used as a printing substrate for multicolor printing (Gurwick, 1932). Another stage in printing of plastics was the emergence of the first plastic films in the 1950s, which were petroleum derivatives. This event has revolutionized the packaging industry as well. Packaging is a major group of plastic materials. Further application areas are shown in Figure 1.1. Transparency of materials, which gives a whole range of promotion opportunities of a packaged product and various barrier properties, resulted in the fact that plastics and, in particular, films are commonly used for packaging manufacturing, both in the form of monofilms, and as multilayer compositions combined with paper and aluminum films.

Figure 1.1  Areas of plastics application in 2013. Source: Own elaboration on the basis of the data (Plastics Europe, 2015).

The largest group of packaging is food packaging, and among these, the most important group is flexible packaging with paper as a forerunner. The advantage of flexible packaging manufactured from plastic over paper packaging, inter alia, depends on better protection against moisture, higher tear strength, a relatively lower price, and the possibility to use modern packaging systems as well as a better product presentation.

Modern packaging is designed to protect the packaged product, promote it, and facilitate its use. Therefore, almost every package requires minimum printing information, although much higher requirements are imposed on the majority of them. Nowadays, when shelves are overfilled with products, packaging plays an important role while shopping. Performance esthetics, unique shape, color schemes, or other visual elements can tempt a hesitant customer to buy a given product. The marketing function of packaging is closely connected with the printing process and print quality. However, printing on plastics means not only printing on food, cosmetic, or industrial packaging, but also printing on everyday objects, electronics, medical devices, sports equipment, advertising gadgets, polyester fabrics, etc.

Multicolored, high-quality printing on plastic material can be made only by appropriate selection of printing techniques and their parameters as well as the type of ink used for a given substrate. Due to the variety of materials available on the market, it is estimated that there are currently >700 types, which are divided into several groups (Plastics Europe, 2014). A knowledge of printing techniques and process requirements concerning the substrate or quality control is thus necessary. The subsequent chapters of this book discuss all these issues.

1.2. Printing Techniques

According to the encyclopedic definition (Rosato, 2000), printing is a method used for decoration and execution of marketing objectives, which are imposed on plastic materials. Various printing techniques are applied for this purpose.

Decoration does not have to be limited to printing with different techniques, but it can also include various indirect methods of imprinting a picture on a material. Therefore, the methods of decorating polymers include the following:

• taking the picture directly on a material using

• conventional printing techniques,

• digital printing techniques,

• hot and cold film stamping,

• taking the picture indirectly on a material using:

• heat transfer,

• aquagraphic, cubic printing,

• in-mold labeling (IML),

• in-mold decoration (IMD) or film insert molding (FIM).

Printing techniques, depending on the character of the printing form used or the lack thereof, are divided into the following:

• relief printing,

• flat (planographic) printing,

• intaglio printing,

• stencil printing,

• digital printing.

Figure 1.2 shows the patterns of printing techniques with application of printing forms. Figure 1.3 demonstrates the division of conventional and digital techniques (Birkenshaw, 1993; Gibson, Rosen, & Stucker, 2010; Gregory, 1996; Kipphan, 2001).

Indirect decoration consists of application of an inscription that was previously made on different substrates on a polymer being decorated or in decoration during processing operations of polymers. Thermal transfer has a broad scope of application. It can be used for marking flat, cylindrical, or object-shaped, for example, rounded and elliptical substrates. It involves transferring of the inscription that was previously made on a polyester or paper substrate by using a hot stamp (flat, cylindrical, or shaped). Techniques that are used for printing of a substrate used in thermal transfer are screen printing, flexography, rotogravure, or ink-jet. The indirect decoration technique is applicable for taking inscriptions on electronic devices, white goods, or cosmetic packaging.

In the case of aquagraphic technology, the inscription is made on a water-soluble film. Image transfer takes place as a result of dissolving of a plastic surface and taking the image floating on the surface of water on a decorated element that is immersed in water. The advantage is the possibility to decorate materials with complicated shapes, which are difficult to decorate using other techniques.

Figure 1.2  Pattern of a printing technique: (a) relief, (b) flat, (c) gravure, and (d) stencil.

IML is one of the decorating techniques used during processing operations. Inscription is performed by printing techniques on a tape or labels that are placed on the form into which the material is injected. Decoration is done by welding the inscription into the structure of the product. This technique is applicable for mass production of both household chemical and cosmetic packaging.

IMD or FIM techniques, in contrast to IML, can be used for decorating complex-shaped products. The print is made previously, usually by the screen-printing technique, on both polycarbonate (PC) and polyester films or on acrylonitrile butadiene styrene (ABS). The films are first thermoformed according to the interior of the mold in which they will be placed. Then, they are placed in the mold, and the material is injected into the mold together with the insertion. This method of decoration is used in the automotive industry, mobile sector (casings and keypads), computer hardware parts, medical equipment, domestic appliances, etc. (Li et al., 2014).

Selection of the decoration technology is done based on the following factors:

• properties of the decorated material;

• destination of the product;

• expected characteristics and performance of the product;

• adhesion of ink used in a given technique to the decorated material and wettability of the material;

• costs and profitability depending on the scale of production;

• expected quality of a printed image and graphic elements.

1.2.1. Flat Printing

In flat (planographic) printing, the printing and nonprinting elements are on the same plane, and the printing process is based on the physicochemical properties of individual elements. Printing areas are oleophilic (i.e., they accept ink), while nonprinting areas are oleophobic and hydrophilic (i.e., they have no ink absorption capacity, but do absorb water).

Figure 1.3  Division of printing techniques.

Flat printing is derived from lithography, which was patented in 1800 by Johann Senefelder (Gregory, 1996). The printing process is based on the repelling properties of water and fats. The drawing is made by using a greasy crayon or special lithographic ink on a polished flat stone called a lithographic stone. Then, it is acidified to obtain oleophilic properties by the printing elements and hydrophilic ones by nonprinting elements. A layer of ink accepted by printing elements is applied on a stone; then the wetted substrate is pressed by using a press. Today, this technique is used in the artistic graphics.

Lithography initiated /gave the begginings of offset printing. It has the widest range of applications, and, in contrast to the original, is not a direct printing technology. Offset printing is an example of indirect printing, that is, the image from the printing form (usually aluminum one) is transferred to the blanket cylinder with a flexible substrate and only then it is applied on printing surfaces. Printing is performed by using paste inks.

A number of offset printing varieties are used. By considering the characteristic of the substrate, one can distinguish between sheet-fed and web-fed offset printing. Web-fed printing, depending on the method of drying the web being printed, is divided into coldset and heatset. The first type of printing is done by ink absorption into the substrate, that is, the printing base must be the absorbent substrate—uncoated papers. In the second case, a drying tunnel is used, where the curing occurs as a result of the influence of air at a high temperature—this variety of offset printing is widely used for printing of coated papers. Another division of offset techniques takes into account the use of a moisturizing solution—water with additives, which is the characteristic feature of the classical offset technique. This is why we identify wet-offset (classical) and waterless offset. The latter, due to elimination of dampening solution from the process and use of silicone forms, is useful for printing nonabsorbent substrates. Detailed information on offset printing has been included in Chapter 13.

1.2.2. Relief Printing

In relief printing, as the name suggests, the printing elements are located above the nonprinting ones. Only the protruded surface elements are inked and then brought in firm contact with the printed substrate.

As of 2015, the main technique of relief printing is flexography. Further, it is the only conventional printing technique, for which a further increase in market share and dynamic development is still recorded. This technique is derived from aniline printing developed in the late-nineteenth century by Bibby and Baron (Gregory, 1996). Aniline printing consisted of using rubber printing plates. The printing was performed using fluid aniline inks. The technique was very simple and relatively cheap, but the print quality was poor, and this method could only be implemented when printing on undemanding materials, mainly paper bags. In 1950, the technique was greatly developed, new inks were introduced, and its name was changed to flexography. The advantage of this technique is the possibility of using both absorbent and nonabsorbent substrates. Simplicity of the technique and current quality comparable with gravure and offset printing make it the most dominant technique for printing on plastic packaging. In recent years, due to competitive prices and expenditure minimization, it significantly replaced gravure printing used for printing on film. Details on the flexographic printing process are specified in Chapter 11.

Typography is the oldest relief printing technique, which was widely used in the 1970s and 1980s. It was actually totally replaced by offset. It involves direct sheet printing with paste inks using a convex metal form.

Indirect relief printing (letterset) is a relief printing technique that combines elements of offset and typography. The transfer of ink from the printing form is carried out as in the offset, using a cylinder covered with rubber, whereas the inks are applied as in typography. Moreover, the machines recall those used in typography, except that an additional blanket cylinder is implemented. Printing plates, however, are made of polymers or thin metal plates. Waterless offset is useful for printing on paper and cloth or plastic. When printing on the latter material, it is used for the production of labels, stickers, wrappers, etc.

1.2.3. Gravure Printing

In intaglio printing, the printing elements are placed below the nonprinting ones. Rotary gravure printing has been used since the eighteenth century, though the modern gravure is developed only since the late-nineteenth century. During the gravure printing process, an ink is applied to the entire surface of the printing plate, whereupon it is scraped from the nonprinting parts. Pressing a plate against the substrate results in transferring ink from the recessed elements of printing plate on a substrate. Production variations of this printing technique are gravure printing, steel engraving, and pad printing (Gregory, 1996; Kipphan, 2001).

The most common technique for this type of printing is gravure. This is a technique for direct, web-fed printing. Sheet-fed gravure is used for special applications when very high quality is expected (PNEAC, 2015). Printing cylinders created using laser engraving technology enable one to obtain very high-quality prints, on both absorbent and nonabsorbent substrates. Unfortunately, due to the cost of their implementation, gravure is used only for high-volume or luxury work. This type of printing concerns colorful, illustrated magazines and catalogs consisting of coated paper as well as packaging—mainly film. Details about this technique are presented in Chapter 12.

Steel engraving printing is a form of gravure printing that is dedicated for continuous tone printing with engraved steel plates. This technique is very time-consuming, and the preparation process is expensive. It is used in a very limited number of European printing houses. Steel engraving printing is used mainly for printing stamps, banknotes, or other securities.

Pad printing, such as offset printing, is a form of indirect printing. The ink is transferred from the printing plate (matrix) to the printed substrate using a silicone stamp, the so-called pad. Selecting an appropriate pad enables printing on not only flat surfaces, but also on ones with different shapes. The technique is applicable to a variety of substrates, particularly nonabsorbents, such as plastics, glass, and metal. It has been described in detail in Chapter 16.

1.2.4. Stencil Printing

Stencil printing, as the name implies, involves application of the ink on a printed substrate using a stencil. The screen printing technique is an example of this method. It is not only applied in printing, but also in artistic as well as textile industries. It is a very old technique that originated in Japan, where stencils were used for decorating kimonos. In America and Europe, screen printing developed at the beginning of the twentieth century. In 1907, Samuel Simon implemented a method of using silk stretched on a frame covered with varnish in places where the ink would not go through the material. During World War I, in the United States, a stencil was made of shellac film, which was then replaced with a cellulose film, which revolutionized the screen printing technique by obtaining higher quality. Screen printing consists of the transfer of ink through the holes in the mesh using a doctor blade sliding over the surface. The fiber mesh of the metal or polymer is stretched on the frame, and a stencil is prepared by manual and/or photomechanical methods. This technique is very simple, and it is possible to use it for printing flat materials as well as ones of different shapes. It also allows much greater thicknesses of applied ink than in the case of other printing techniques and can be used to print all kinds of substrates, including plastic (Birkenshaw, 1993; Kipphan, 2001). More information concerning screen printing can be found in Chapter 15.

1.2.5. Digital Printing

Digital printing is the newest printing technique. The substrate is printed on the basis of the information stored on a computer in the form of digital data. Contrary to previously characterized techniques, this one completely excludes printing plate or such a plate is created just prior to each print. This makes it possible to obtain the unique characteristics of each printing, for example, through their personalization. A variety of digital printing are shown in Figure 1.3. In addition, it can be classified according to the printing system: printing using ink and using toner. Depending on the technology, wet and dry toners and various types of ink cartridges can be applied. This creates the possibility of processing the print immediately after the printing process. An appropriate choice of technology and toners or inks makes it possible to print not only on absorbent substrates, but also on nonabsorbent ones. For plastic substrates, ink-jet, as well as electrophotography, and thermal transfer are mainly used. According to PIRA forecasts (Page, 2011), the use of digital technology in printing on flexible packaging will increase in the coming years.

Ink-jet printing includes the use of fluid inks of a low viscosity. Depending on the type of ink, the following printing types may be determined: latex, solvent (and its variants: solvent, mild solvent, ecosolvent), pigment, dye, and ultraviolet (UV). In contrast, depending on the transfer of a specific ink type, the following types are distinguished: continuous ink-jet and drop-on-demand. Ink-jet printing is a technology that allows the execution of printing on a wide range of substrates that range from paper by metals and glass to plastic. The printing process is determined by the properties of the ink used, particularly viscosity and surface tension. Plastic printing applies primarily to UV and solvent technologies. The surface free energy of the polymer substrate should amount to at least 35  mJ/m² (Gibson et al., 2010; Gregory, 1996; Müller et al., 2014). Issues related to ink-jet printing are discussed in Chapter 14.

Electrophotography, also called xerography, is the primary technique used in photocopiers and laser printers. This is the most commonly used toner printing system. Others include ion deposition (ionography), electrostatic, magnetographic (magnetography), and electrographic (electrography). Electrophotography involves the removal of negative charges by the use of light from the surface of a photosensitive cylinder, which is then covered with the toner. The toner has a negative charge and covers the surface of the cylinder in places where the charge has been removed, thereby creating a reproduced image. The image is then transferred to a positively charged substrate surface, which is moved under the cylinder. The transferred toner is fixed on the printed substrate by heating, or heating and pressure. The cylinder is cleaned of the remaining toner and negatively charged. The process is repeated to perform the next printing (Birkenshaw, 1993). Printing is actually performed on paper. It is possible to implement EP to print some of the films and film labels.

There are two variants of thermal transfer printing: a direct printing of a special substrate allows the simple transfer of the image to the right substrate and printing using the ink ribbon. The first thermal transfer printing method, known as sublimation, is a form of indirect printing. A print is made on a special paper for thermal transfer printing using an ink-jet printer with ink dedicated to these applications. Then, the printed image is transferred from the printed paper substrate by using a high temperature press. This technique is used primarily to perform printing on fabrics, including polymer fabrics (e.g., flags, textile banners). The second method is a direct method. A dye from the ribbon is transferred under heat to the printed substrate. This method is applicable when printing on labels, including those made of plastic.

1.2.6. Three-Dimensional Printing

Beyond 2D printing, which is accomplished by using the previously described traditional or digital printing techniques, 3D printing is now becoming more and more important. It is not a case of applying ink to a substrate to create a flat or relief structure of the image (using a large thickness of ink in the case of ink-jet and screen printing to obtain relief elements of Braille or warning signs, or using the so-called special inks: swelling inks applied in screen printing for advertising purposes), but to create a spatial object. Three-dimensional (3D) printing is a very recent technique, as its origins date back to 1980, but it is developing dynamically. It involves the production of 3D spatial objects based on a digital model. Plastic and biodegradable materials are used for printing, which now already enables the creation of multicolored objects. Also, metals or ceramics may be applied, and currently, a research on the combination of different materials is being conducted. Recently, the three most widely used 3D printing techniques include laser sintering, laser melting, and laser metal deposition (Gibson et al., 2010; Wang & Liu, 2014). Chapter 18 includes more information on the available 3D techniques and their applications.

1.2.7. Hybrid Printing

Hybrid printing consists of combining two different printing techniques in one process. This can be done through a combination of used printing units or two types of inks with different properties (Wang & Liu, 2014; Wu et al., 2012). Either two conventional techniques, or two digital, or both conventional and digital techniques (most commonly used) may be combined.

The possible combination is flexography and ink-jet. Thanks to this, a package may have unique characteristics, or printing can be easily adapted to the target group (Niga et al., 2012). Ink-jet is also commonly combined with an offset and enables printing of the final personalization or numbering. Another example is the combination of digital technology, combination of electrophotography with classical offset printing, where a toner is replaced by fluid ink. The use of such a hybrid machine creates the possibility of printing on a much wider range of substrates than in the case of classical electrophotography. Substrates such as metalized films or heat-sensitive copy forms can be used.

It is also common to combine flexography, screen printing, and offset printing in the production of labels. Screen printing is used, for instance, for preprinting on transparent film with white ink, that is, the so-called ground print, which is then covered with a multicolor flexographic print. Another application is creating relief warning signs on the label that was printed using flexography. Another combination may involve the use of a screen-printing unit to varnish the flexographic material or to coat the final prints using a flexographic printing unit in an offset printing machine (Kipphan, 2001).

The use of hybrid printing provides the subsequent processing advantages such as optimization of processes, minimization of time, or the creation of new production capacity.

1.2.8. Various Printing Techniques for Polymer Decoration

Printing is one of the basic material processing technology, next to dyeing, painting, decorating, metalizing, and laminating. Not every printing technique can be applied to all types of materials. Techniques such as pad printing, screen printing, and waterless offset are mainly used for printing on plastic products of various shapes, and for 3D ones. Offset, flexographic, and digital printing, however, depending on the technology, are carried out on a plastic sheet and a roll. Gravure is used primarily as a web-fed printing, usually for printing high-quality packaging films, used for the production of luxury packaging produced on a large scale. Table 1.1 shows the suitability of the various printing techniques to print selected polymeric materials and packaging materials.

1.3. Printing Bases

Printing, depending on the selected printing technique, can be performed on almost any type of material. The primary medium is printing paper and cardboard. The next most common ones are plastics. Other materials that can be printed are metal, glass, and textiles.

Substrates, because of their rigidity, are classified as flexible, semirigid, and rigid. Flexible substrates are materials with a thickness of <25  μm, which are available in the form of a roll and printed using web-fed presses. These include plastic films, films of biodegradable materials, and laminates. Examples of semi-rigid materials are more rigid films and laminates with a thickness of 25–150  μm, printed on web-fed or sheet-fed presses, or printed as a finished product. They are used for the production of tubes, containers, and trays, commonly produced by using thermoforming techniques. Rigid substrates include plastic bottles, boxes, transport boxes, containers, and plates.

Table 1.1

Printing Techniques for Selected Types of Packaging and Materials

+: High usefulness.

+/−: Usefulness after taking into consideration certain restrictions.

Source: Own elaboration on the basis of Izdebska (2012).

1.3.1. Films

Films are materials with a nominal thickness not exceeding 250  μm. They are the largest group of products made of plastic and are mainly used in the packaging market (Rosato, 2000). Monofilms are homogeneous films made of one material. Beyond these, multilayer films, described in Section 1.3.2, are commonly applied in the market.

Plastic film is most often manufactured as follows:

• blow molding of a sleeve: the molten material is extruded through a circular aperture, and air pressure gives it the form of a sleeve;

• casting, or flat slotted extrusion: molten material is extruded through a flat die and cast on a cooled cylinder.

To manufacture a film for printing purposes, the following are primarily used:

• plastics such as

• polyethylene (PE),

• polypropylene (PP),

• polyethylene terephthalate (PET),

• polyvinyl chloride (PVC),

• polyamide (PA),

• polystyrene (PS),

• PC,

• biodegradable plastics such as

• polylactide (PLA),

• cellulose,

• products based on starch.

To improve the properties of films, they are often subjected to monoaxial or biaxial orientation. Orientation of a film is its stretching in a certain way, which depends on the manufacturing process and the type of polymer. Biaxially oriented PP films are most commonly used as substrates and packaging materials. Also, polyester films are often subjected to orientation. This method improves their barrier properties to water vapor and gases and strength—tear resistance and tensile strength (Emblem & Emblem, 2012).

Films, if they are not dyed in mass, are originally transparent substrates. Often onto transparency film addition to multicolored printing also underprint is performed. If the entire surface of the film is to be printed in color and is intended to be a nontransparent material, films are originally dyed in mass with white color.

A special version of films are metalized films. They are applied in laminate manufacture, improving the barrier properties of films to gas and water vapor, and in providing a barrier to UV radiation. Most commonly, metallization involves the application of a thin layer of aluminum on the material. It is made primarily for PET and PP films and biodegradable PLA. Metalized films are a special group of substrates, which requires the use of different control devices for checking the quality of the print. This is due to silver, high-gloss film, which requires a spherical geometry for measuring color.

Thermoshrink films are also worth mentioning. They are produced from monoaxially oriented films of polyvinyl chloride (PVC), polyethylene terephthalate (PET), polyethylene terephthalate glycol-modified (PETG), and oriented polystyrene (OPS). They are used for packaging of individual products (e.g., laminating books) or bulk packaging (e.g., six bottles of water wrapped in film), and for labeling the so-called shrink sleeve labels, for instance, labeling of plastic bottles and cups for dairy products. Heat-shrinkable films are printed with flexography; then a heat shrink sleeve is prepared, which is cut into individual labels. In the next stage, labels are placed on the product, on which they are to be shrunk. High-temperature leads to adoption of the shape of the packaging on which the labels are placed (Abdel-Bary, 2003; Elsayed, 2003; Emblem & Emblem, 2012).

Most films before the printing process require the preparation of their surface. Especially films having the widest application in the packaging industry—PP, PE films before printing must undergo activation in order to raise their very low surface free energy values. The most extensive industrial use is corona activation, often performed immediately before printing with a printing press. The film can also be activated by the manufacturer and delivered as already prepared for printing, but it should be remembered that the stability of the activation is limited. After some time, the energy raised in this way will decrease—initially, rapidly and then more slowly. Printing on films is performed by flexography or gravure.

1.3.2. Multilayer Films

Multilayer films are also called complex films and those obtained in the lamination process are called laminates. However, frequently all such films are commonly called laminates. Laminates next to plastic films are one of the basic polymeric substrates. They are manufactured by combining two or more plastic films, or any combination of plastic film (typically PE, polyester, PP, cellulose, or PA), with aluminum film or paper products. The use of laminates enables one to combine the properties of each used layer. Usually, it is from two to five layers. The materials are joined together by gluing, calendering, or coextrusion. A proper selection of the individual layers of sometimes extremely different physicochemical properties and barrier properties makes it possible to obtain a material with almost any characteristics. Application of an aluminum foil between polymer films provides a complete barrier (Shishir & Vinay, 2010).

Printing on multilayer films is usually performed using flexography or gravure. Printing can be done on the surface or an interlayer (Figure 1.4). The surface method has a different character, which depends on the rigidness of the material. Flexible laminates are printed as a finished material. In the case of semirigid and rigid multilayer films, the surface film is printed, and it is then combined with the other layers of the laminate. However, interlayer technology involves placing a printing between the films. This is performed in two ways: The first method is widely used in the packaging industry and involves a reversely printed top film (the inner side). The second method is used while printing on the surface of the second film, forming a part of the laminate. In both methods, the laminate is made only after the film has been printed. The main benefits of this type of printing are protection against mechanical damages using film as a component of a laminate, more gloss, and elimination of direct contact of the ink with the wrapped product.

1.3.3. Semirigid and Rigid Plastic Sheets

Sheets are produced by extrusion process using a slit nozzle. They can be extruded as a single layer or as multilayer materials (coextruded). In the case of coextrusion, several nozzles are used (depending on the number of layers), of which at the same time individual materials are extruded, to form single layers of a sheet. Apart from solid sheets, expanded sheets can be produced. Examples of commercially available sheets are A-PET/PE, PVC/PE, PP/EVOH, PP, and PE suitable for sterilization and pasteurization, expanded polypropylene/EVOH/PP expanded for pasteurization and microwave, expanded EPET/PE, and PS/PE.

The parameters characterizing the sheet depend on the selection of the nozzles. Through their selection, their thickness, width, and material properties are determined. The largest applications have sheets with a thickness of 150–1600  μm. The achieved sheets are usually not subjected to orientation and are used for further processing operations involving the product's thermoforming.

The extruded products may undergo printing after their formation, although the dominant method of decorating is labeling. A print can be performed using waterless offset printing, screen printing, or it can be performed digitally on the surface of the item that has usually undergone prior corona activation. Labeling may be done in a form or by placing a label in separate processes. The first solution provides the best quality and causes that during the manufacturing phase a ready printed item is obtained. Further, thermoformed products can be made of colored sheets at the stage of their extrusion (Emblem & Emblem, 2012).

Figure 1.4  Laminate printing: (a) surface, (b) interlayer with reverse printed top film, (c) interlayer with the second top film printed.

1.3.4. Injection Molded Products

Products made with injection technique have very different shapes and sizes. They are produced by injection of plasticized polymer under high pressure to the form. Beverage bottles and other yoghurt cups, containers of various types, caps, and tubes are manufactured in this way.

Such products are often decorated by in-mold labeling. This method is more applicable to items produced by this method than by thermoforming. Another important way of decorating is labeling, especially the use of preprinted shrink labels (shrink sleeve labels). They allow covering of all or part of the surface of the container, adapting perfectly to the shape by shrinking due to temperature. They are commonly used for containers and bottles of chemicals, cleaning products, cosmetics, beverage bottles, liquid milk products, cheese cups for yoghurts, desserts, tubes, etc. The use of such labels is also beneficial for environmental reasons—it is possible to easily separate a label from the package, to make waste disposal easier. Also, traditional techniques of printing directly on the product may be applied, but they are used in the case of low-cost production, not mass production. Printing on injection molded products can be done primarily using the following techniques: screen printing and pad printing, waterless offset, or digital thermal transfer. Before printing, the product usually requires activation. Two methods of activation are generally used: corona and flaming (Coles, McDowell, & Kirwan, 2003; Emblem & Emblem, 2012).

1.3.5. Synthetic Papers and Polymer-Coated Boards

Synthetic papers mock paper made of polymers. Since they are made of a polyolefin (PP or PE), they have, unlike paper, very good resistance to tearing, the impact of UV radiation, or water, chemicals, and grease. Their main use is the production of maps, instructions, IML labels, labels for products, covers of books for children, or their pages, etc. Printing and further finishing of synthetic paper after printing is the same as for ordinary paper (Lin & Cheng, 2014; Toyoda et al., 1987). When performing printing, the ink should be well considered (oxidative or UV). In the case of oxidative inks, a much longer time for their fixation on the substrate than in the case of conventional inks and papers should be taken into account. The pile height on covering (not too high) and environmental conditions must also be controlled and properly matched. Synthetic paper is primarily printed applying the following techniques: offset and ink-jet and also flexography, gravure, and screen printing.

Cartoons coated with polymers have different functional properties. The polymeric coating provides the paper with improved barrier properties and mechanical properties as well as allows the welding of the material. For example, packaging used for milk to ensure barrier properties is made of laminated materials. An extrusion lamination is widely used for the production of coated cardboard packaging, where the box is coated with polyolefins. A low-density polyethylene is used above all for coating and also other materials are used (high-density polyethylene, green PE, PP, oriented polypropylene, PET, and PLA). Beyond coating, extrusion lamination can also be used; this consists of combining a cardboard with a polymer film by a melted polymer used as the adhesive layer. Coated cartons are widely used in the production of packaging and paperback books.

These substrates can be printed by implementing offset printing, ink-jet, electrophotography, or flexography. Due to possible problems concerning moistening of the polymeric substrate and the adhesion of ink, the polymer layer is prepared before printing. This happens through application of primers, varnishes, or through activation. Primers and varnishes (aqueous or solvent) are applied directly before printing or may be applied by the manufacturer of the substrate. If, in order to increase the surface free energy of polyolefins corona activation is used, corona treatment/activation is executed directly on the printing press (Haenen, Resch, & Scholte, 2012; Katan, 1996; Rentzhog 2006).

1.4. Printability

The primary factors that determine the printability are substrate properties, determined by its porosity, and surface properties, determined by surface free energy (SFE) (López-García et al., 2013). Other properties of the substrate, which influence the process of printing, are as follows:

• structural and dimensional, including thickness, smoothness, and surface cohesion;

• durability, such as breaking load, extensibility, rigidity, hardness, and resistance to bending;

Figure 1.5  Different levels of wettability.

• optical, whiteness, opacity, and color;

• hydrophobic and hydrophilic, such as water absorbability or dimensional stability.

Porosity is significant for permeability due to substrates ability to absorb inks or lacquers or other liquid and paste substances. It is determined by the size and amount of pores on the substrate. Plastic substrates, unlike uncoated paper with high porosity (macroporous), are nonporous or very slightly microporous materials. Due to this fact, they are nonabsorbent substrates (Kipphan, 2001; Leach et al., 2007).

In the case of plastic substrates, the key factor that determines the printability is their surface free energy, which is decisive for material wettability and adhesion of the ink to the substrate. In the case of a ready print, surface free energy has an impact on thickness of the ink layer, that is, on the value of the optical density of the print. Besides an appropriate SFE value for the substrate, it is also important to choose an ink with an appropriate level of surface tension. One should always remember that surface tension of the ink should be lower than surface free energy of the substrate. Some practitioners and academics state that the difference between these values, amounting to at least 10, guarantees good printability for a particular set of ink substrates (Bassemir & Krishnan, 1991; Morsy et al., 2006). However, on the basis of their own work, some researchers have stated that it is not always a determinant (Izdebska, Podsiadło, & Harri, 2012).

To sum up, printability of polymer substrates may be improved by the following:

• increase in surface free energy of the material, as a result of its activation;

• reduction of surface tension of applied inks;

• the maximum reduction of the polar component of substrate SFE.

1.5. Surface Wettability

Wettability is one of the basic features of printing substrates that depends on chemical content and material morphology. Inks may spill on the surface or remain on it in the form of a drop (Figure 1.5). Spilling of ink is a sign of full wettability of the substrate. If it remains in the form of a drop, the level of wettability is determined by the contact angle, that is, the angle made by the drop with the substrate (Figure 1.6). If the angle is <90° it means that the wettability is good. A bigger angle refers to low wettability. No wettability exists when the drop stays fully on the material surface (Tian, Song, & Jiang, 2013; Yuan & Lee, 2013; Zielecka, 2004).

To improve the wettability of plastic surfaces, they are subject to various methods of modification of the cover layer, as follows:

• corona discharge in air;

• flame activation;

• UV radiation, X-ray, laser radiation, and radiation of high-energy electron beam;

• application of low-temperature plasma generated with partial discharge occurring in the atmosphere of various gases, at a lowered pressure;

• chemical effect of acid solutions and hydrolysis of a cover layer;

• application of reactive gases (chlorination, sulfonation, fluorination, chlorosulfonation, and oxidation);

• radiation or photochemical bud of this surface.

The most common method is corona discharge (Żenkiewicz, 2000).

1.5.1. Surface Tension of Inks

The surface tension of inks influences the wettability of the substrate and printability. This depends on the type and composition of ink. Polar liquids are characterized by high surface tension and the nonpolar one has low surface tension. Due to this fact, inks in which water is used as a solvent (73  mN/m) will have higher values, and those, which include ethyl alcohol (24  mN/m) or other nonpolar solvents, will be lower. For example, surface tension values of flexographic water-based inks range from 34 to 38  mN/m, whereas solvent-based ones range from 28 to 32  mN/m (FFTA, 1999). The values for ink-jet inks are more differentiated and vary from 22 to 45  mN/m. Offset and lithographic inks have a surface tension of about 37  mN/m (Leach et al., 2007). For example, in Figure 1.7, there is a drop of flexographic, solvent-based, and water-based ink of the same volume placed on the same polymer substrate—the solvent-based ink with a lower surface tension moistens the material better.

Figure 1.6  Different surface wettability.

Surface tension is a force tangential to the surface which has an effect on the length unit (meter newton per meter). One of the methods for defining surface tension used in printing is a strain gauge (e.g., ring Du Noüy method). It consists of torque measurements of force that are necessary for dragging the surface of the ring, made from a thin platinum wire, from the surface of the examined liquid. This ring is kept in place by force of surface tension (Kigle-Boeckler, 1991).

1.5.2. Surface Free Energy of Printing Substrates

The value of surface free energy (mJ/m²) of plastic products is defined on the basis of the contact angle obtained for different measurement liquids. The basis for the calculations constitutes the Young Equation (1.1) (Young, 1805):



σSV is the surface tension of the solid body in balance with saturated steam of liquid,

σSL is the interphase surface tension of the solid body and liquid,

σLV is the surface tension of the liquid in balance with the saturated steam of this liquid,

ΘY is the equilibrium contact angle.

Defining the surface free energy directly from Eq. (1.1) is only possible after simplifying of the assumptions. There are many methods for defining the SFE value for polymer materials. These were developed by Berthelot, Antonow, Girifalco and Good, Neumann et al., Fowkes, Zettlemoyer, Owens and Wendt, Wu, van Ossa-Chauhury-Good, Zisman. These methods assume application of various assumptions and measurement liquids. This is why the defined SFE values are not comparable. Especially, in the case of modifiable substrates, the differences may be significant. In practice, for flat plastics, the most common method used is the Owens–Wendt method, in which two liquids with a known surface tension—polar (water) and nonpolar (diiodomethane) ones—are used (Żenkiewicz, 2007).

Polymers with the lowest values of surface free energy are polyolefins. Their printing and inward processing are only possible when the cover layer is modified. The values of surface free energy of the chosen nonmodifiable polymer films are presented in Table 1.2. Devices for Measurement of the Contact Angle

The most common technique of contact angle measurement is the direct measurement of the static angle of wetting at the point of contact of three phases of a drop on the substrate. Such measurements with the application of various measurement liquids may be conducted on goniometers (Yuan & Lee, 2013). The most common measurement liquids used are water, diiodomethane, and ethyl glycol (Figure 1.8).

Figure 1.7  Comparison of wetting the polymer substrate with (a) water-based and (b) solvent-based inks.

Table 1.2

Values of Surface Free Energy of the Chosen Films

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