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Multilayer Flexible Packaging

Multilayer Flexible Packaging

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Multilayer Flexible Packaging

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5/5 (3 évaluations)
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1,146 pages
359 heures
Sortie:
Mar 29, 2016
ISBN:
9780323477185
Format:
Livre

Description

Multilayer Flexible Packaging, Second Edition, provides a thorough introduction to the manufacturing and applications of flexible plastic films, covering materials, hardware and processes, and multilayer film designs and applications. The book gives engineers and technicians a better understanding of the capability and limitations of multilayer flexible films and how to use them to make effective packaging.

It includes contributions from world renowned experts and is fully updated to reflect the rapid advances made in the field since 2009, also including an entirely new chapter on the use of bio-based polymers in flexible packaging. The result is a practical, but detailed reference for polymeric flexible packaging professionals, including product developers, process engineers, and technical service representatives.

The materials coverage includes detailed sections on polyethylene, polypropylene, and additives. The dies used to produce multilayer films are explored in the hardware section, and the process engineering of film manufacture is explained, with a particular focus on meeting specifications and targets. In addition, a new chapter has been added on regulations for food packaging – including both FDA and EU regulations.

  • Provides a complete introduction to multilayer flexible packaging, assisting plastics practitioners with the development, design, and manufacture of flexible packaging for food, cosmetics, pharmaceuticals, and more
  • Presents thorough, well-written, and up-to-date reviews of the current technology by experts in the field, making this an essential reference for any engineer or manager
  • Includes discussion and analysis of the latest rules and regulations governing food packaging
Sortie:
Mar 29, 2016
ISBN:
9780323477185
Format:
Livre

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Multilayer Flexible Packaging - Elsevier Science

2007.

Part I

Introduction

Outline

1 Introduction

1

Introduction

John R. Wagner Jr.¹ and Scott B. Marks²,    ¹Crescent Associates, Inc., Rochester, NY, United States,    ²E.I. du Pont de Nemours & Co., Wilmington, DE, United States

Abstract

Multilayer films have their history of development steeped in the depths of the development of plastic films and resins. From the early concept of a desire for a non-staining table cloth arose the thought processes that lead to cellulosic films such as cellophane, and onward into the world of many polymers such as polyethylene, polypropylene, polystyrene, and nylon. Many other polymers followed suit, leading to a revolution in the world of plastics and their many downstream uses.

This chapter gives a historical perspective of plastic films, presents some data on the global economy and looks at materials, the processes used, requirements, barrier and sealability.

Keywords

Polyethylene; polypropylene; polyester; polystyrene; coextrusion; tie resins; EVOH; Nylon; barrier films; multilayer films

1.1 Materials: A Historical Perspective

Today we have many clear plastic packaging films. Jacques E. Brandenberger invented the first common clear film, cellophane in 1908. He was a Swiss textile engineer whom first thought of the idea for a clear, protective, packaging layer in 1900. He was seated at a restaurant when a customer spilled wine onto the tablecloth. As the waiter replaced the cloth, Brandenberger decided that he would invent a clear flexible film that could be applied to cloth, making it waterproof.

Brandenberger experimented with different materials and tried applying liquid viscose (a cellulose product known as rayon) to cloth, but the viscose made the cloth too stiff. His idea failed but he noted that the coating peeled off in a transparent film. Like so many inventions, the original use was abandoned and new and better uses were found. By 1908 he developed the first machine to manufacture transparent sheets of regenerated cellulose. By 1912 he was making a saleable thin flexible film used in gas masks. He obtained patents to cover the machinery and the essential process ideas [1]. The rights to produce cellophane were then obtained by E.I. du Pont de Nemours & Co, who began to produce and further refine the process for producing cellophane. Breakthrough improvements included adding a moisture barrier layer to the cellophane, in the form of a nitrocellulose coating. This allowed for better stiffness retention in the cellophane and facilitated using the film as a food overwrap film. This coating was then refined to make it heat sealable as well, creating the first readily sealable packaging film. Later on, other coatings were applied to cellophane including PVDC (polyvinylidene chloride), which added oxygen barrier and moisture barrier to the cellophane, resulting in the original nonmetal barrier film for food packaging.

Today we have many polymers such as PE (polyethylene), PP (polypropylene), PET (polyester), and PS (polystyrene) that are used to produce clear films for packaging. While these aforementioned polymers are commonly used in monolayer format, they are also used in multilayer films produced by coextrusion and/or lamination processes. There also exist many specialty polymers and compounds, which sometimes are used monolithic, but are more commonly used in coextrusions.

Polyethylene was first synthesized by the German chemist Hans von Pechmann who prepared it by accident in 1898 while heating diazomethane. When his colleagues Eugen Bamberger and Friedrich Tschirner characterized the white, waxy, substance that he had created, they recognized that it contained long –CH2– chains and termed it polymethylene [2].

The first industrially practical polyethylene synthesis was discovered (again by accident) in 1933 by Eric Fawcett and Reginald Gibson at the ICI works in Northwich, England. Upon applying extremely high pressure (several hundred atmospheres) to an ethylene and benzaldehyde mixture, they again produced a white, waxy, material. Because the reaction had been initiated by trace oxygen contamination in their apparatus, the experiment was, at first, difficult to reproduce. It was not until 1935 that another ICI chemist, Michael Perrin, developed this accident into a reproducible high-pressure synthesis for polyethylene that became the basis for industrial low-density polyethylene (LDPE) production beginning in 1939 [2].

Subsequent landmarks in polyethylene synthesis have revolved around developing several catalysts that promote ethylene polymerization at more mild temperatures and pressures. The first was a chromium trioxide–based catalyst discovered in 1951 by Robert Banks and J. Paul Hogan at Phillips Petroleum. In 1953 the German chemist Karl Ziegler developed a catalytic system based on titanium halides and organoaluminum compounds that worked at even milder conditions than the Phillips catalyst. The Phillips catalyst is less expensive and easier to work with; however, both methods are used in industrial practice.

By the end of the 1950s, both the Phillips- and Ziegler-type catalysts were being used to produce high-density polyethylene (HDPE). Phillips initially had difficulties producing a uniform quality HDPE product and filled warehouses with off-specification plastic. However, financial ruin was unexpectedly averted in 1957, when the hula hoop, a toy consisting of a circular polyethylene tube, became a fad among youth in the United States.

A third catalytic system, one based on metallocenes, was discovered in 1976 in Germany by Walter Kaminsky and Hansjörg Sinn. The Ziegler and metallocene catalyst families have since proven to be very flexible at copolymerizing ethylene with other olefins and have become the basis for the many polyethylene resins available today, including very low-density polyethylene and linear low-density polyethylene. These new catalysts have allowed creation of some very special polyethylene resins. One such example is the polymer used to produce DSM’s Dyneema fiber, an ultra high-strength material that competes with aramid-based fibers in applications where high strength is needed, but not where high temperature resistance is also needed. As it has always been, new materials find their useful niches in the market.

Until recently, the metallocene systems were the most active single-site catalysts for ethylene polymerization known. New catalysts are typically compared to zirconocene dichloride. Much effort is currently exerted on developing new, single-site (so-called postmetallocene) catalysts that may allow greater tuning the polymer structure than is possible with metallocenes. Recently the work by Fujita at the Mitsui Corporation (among others) has demonstrated that certain salicylaldimine complexes of Group 4 metals show substantially higher activity than the metallocenes [2].

Dr. Karl Rehn at Hoechst AG in Germany first polymerized polypropylene in 1951 and did not recognize the importance of his discovery. It was then rediscovered on March 11, 1954, by Giulio Natta [3]. Biaxially oriented polypropylene (BOPP) was introduced in the 1960s. Initially, it was developed in a blown film process, and the first commercial production was started by DuPont in IA, USA. Eventually other companies started to produce BOPP in a cast sheet/orientation process which made the film production more economical. This change was instrumental in replacing cellophane, as it was lower cost and more environmentally friendly to produce. As BOPP usage gained in the industry, there was a corresponding decline in cellophane usage and production. Today cellophane production is a mere fraction of what it once was.

British chemists, John Rex Whinfield and James Tennant Dickson, employed by the Calico Printer’s Association of Manchester, patented polyethylene terephthalate (also called PET or PETE) in 1941, after advancing the early research conducted by Wallace Carothers of DuPont. They saw that Carothers’s research had not investigated the polyester formed from ethylene glycol and terephthalic acid. Polyethylene terephthalate is the basis of synthetic fibers such as generic polyester fiber and specialty fibers such as Invista’s Dacron. Whinfield and Dickson along with inventors W.K. Birtwhistle and C.G. Ritchie also created the first polyester fiber called Terylene in 1941 (first manufactured by Imperial Chemical Industries or ICI). The second polyester fiber was DuPont’s Dacron (now an Invista Corporation product) [4].

Polystyrene was discovered in 1839 by Eduard Simon [5], an apothecary in Berlin. From storax, the resin of the Turkish sweet gum tree (Liquidambar orientalis), he distilled an oily substance, a monomer which he named styrol. Several days later, Simon found that the styrol had thickened, presumably from oxidation; into a jelly he dubbed styrol oxide (Styroloxyd). By 1845 English chemist John Blyth and German chemist August Wilhelm von Hofmann showed that the same styrol transformation took place in the absence of oxygen. They called their substance metastyrol. Analysis later showed that it was chemically identical to Styroloxyd. In 1866 Marcelin Berthelot correctly identified that forming metastyrol from styrol was a polymerization process. About 80 years went by, before it was realized that heating styrol starts a chain reaction which produces macromolecules, following the thesis of German organic chemist Hermann Staudinger (1881–1965). This eventually led to the substance receiving its present name, polystyrene.

The company I.G. Farben began manufacturing polystyrene in Ludwigshafen, Germany, about 1931, hoping it would be a suitable replacement for die-cast zinc in many applications. Success was achieved, when they developed a reactor vessel that extruded polystyrene through a heated tube and cutter, producing polystyrene in pellet form.

In 1959 the Koppers Company in Pittsburgh, PA, developed expanded polystyrene (EPS) foam [5].

Other polymers used in the packaging industry have had similar invention stories ranging from purely accidental discovery to hard-wrought research.

1.2 Markets: A Global Economy

The dynamics of the industrialized nations post–World War II have led to a plethora of applications for many polymers from the mid-20th century continuing into the 21st century. The flexible packaging industry has been one significant part of this growth engine, and adoption for use in many applications has expanded into a global economy, as many newly industrialized nations have become global players in trade.

Table 1.1 [6] shows the flexible plastic packaging films market (in million pounds) in the United States for three packaging films for the years 2002, 2007, and 2012.

Table 1.1

Flexible Plastic Packaging Films Market in the United States: Breakdown of Volume Sales by Material Type for the Years 2002, 2007, and 2012 (in Million Pounds)

Fig. 1.1 plots this data and shows a trend line for the total film market. This exponential fit trend line calculates a 4.1% growth rate from the 2002 to 2012 data. At this growth rate, the US flexible packaging film market could be 20 billion pounds in 2022. This is a slower growth rate than predicted in the first edition with the 2002 and 2007 data. The business recession of 2008–10 likely explains the lag in growth from 2007 to 2012. Another difference is the drop in the PP volume and the dramatic increase in the thermoplastic polyester volume. These numbers have not been confirmed, and like any statistical data they may get revised. It is possible that the PET data is correct as Mitsubishi has announced that they will spend $100 million to expand its Greer, S.C., facility with the installation of a new BOPET stretch film line due to start running in mid-2017. This new line will add 55 million pounds per year of capacity. No further project details are available at this writing. Toray Films in Rhode Island has also expanded production of BOPET in the United States which could explain part of the uptick for the United States.

Figure 1.1 Flexible Packaging Film Market in the United States - Sales Volume versus Year.

Selected data from the US Census Office for the NAICS code 326112 (unsupported plastics packaging film & sheet mfg.) is shown in Table 1.2 [7]. In addition to this selected data, the total value shipments have been adjusted to 1997 dollars using data from the Misery index website [8].

Table 1.2

Selected Data from the US Census Office for the NAICS Code 326112 (Unsupported Plastics Packaging Film & Sheet Mfg.)

Fig. 1.2 plots the data in Table 1.2 for employees, total value shipments, and the adjusted total value shipments to 1997 dollars versus year. The exponential curve fits calculate the total value shipment growth rate at 7.9% and the employee growth rate at 4.6%. When the total value shipments are adjusted to 1997 dollars, the calculated growth rate is 5.5%. These projections are below what was calculated in the first edition which were for total growth 9.16%, employees 6.96%, and adjusted to 1997 dollars 6.73%. This suggests that the market growth rate is down about 1%, employee growth down 2.4%, and adjusted to 1997 growth down 1.2%. This could be due to many factors such as increased market penetration, inflation, and lower raw material costs. The lower employee growth versus sales suggests higher productivity. The drop between 2012 and 2013 may be a trend or statistical variation. One would not know without a better understanding of how the data was taken and reported. Time will also provide an answer.

Figure 1.2 Shipment Value and Number of Employees versus Year

If one were to do a more rigorous future growth estimate, one would have to have good historical sales and population data. Market growth is a function of market penetration, that is, pounds of material used per person and number of people. Looking at global data one would find that there are countries with minimal market penetration, some with average market penetration, and some where the flexible plastic packaging value add is highly recognized and are leaders in taking advantage of the benefits flexible films give.

A market research report on companiesandmarkets.com is predicting that the plastic film market in the United States will grow at 16.65% CAGR during 2015–19 [9]. From this report, they offer some new insights for the US Plastic Film Market¹:

Plastic films are used for packaging chemicals, consumer goods, F&B, and pharmaceutical products. These films are lightweight, non-corrosive, relatively cheap, and can be molded into various shapes, making them highly applicable for packaging. Their inert nature and ability to preserve products for a long period make them a popular choice in the F&B industry. They are also used by other industries for packaging of products, such as automotive parts, industrial goods, pharmaceutical products, and other consumer goods. The various materials used in the manufacturing of packaging films are BoPET, BOPP, cellulosic, CPP, EVOH, HDPE, LDPE, LLDPE, PVC, PVDC, PVOH, and polyamide.

Analysts recognize the following companies as the key players in the Plastic Films Market in the US: AEP industries, Amcor, Bemis, Berry Plastics, Jindal Poly Films, Printpack and Sealed Air.

Other Prominent Vendors in the market are: Allied Plastics, ALPLA-Werke, Ampac, APPE, Britton Group, CharterNex Films, Coveris (formerly Exopack), Daibochi Plastic, DS Smith, GP Plastics, Graphic Packaging, International Precision Components, King Plastics, Northeast Packaging Company, Sigma Plastics, and Tegrant Alloyd Brands

Biodegradable plastic films are easily decomposed by microorganisms. They have a significantly less harmful effect on the environment than conventional plastics. They are not necessarily entirely made from renewable materials; many are made from petrochemicals with biodegradable additives. The adoption of these materials, such as polyvinyl alcohol, polyanhydrides, and polylactic acid, by plastic film manufacturers will reduce the market shares of conventional plastic manufacturers. With environment compliance regulations worldwide becoming more stringent, vendors will be forced to in order to avoid paying significant penalties.

According to analysts, demand for blister packs has been increasing in the pharmaceutical industry in the US. The growing incidence of diseases, the aging population, concern for health and wellness, and changing consumer lifestyles have increased the need for pharmaceuticals, which has in turn led to high demand for blister packaging. The implementation of FDA regulations, which require that all prescribed pharmaceuticals dispensed in hospitals and nursing homes be packaged in unit-dose formats with barcodes to reduce dispensing errors, has increased the sales of blister packs over the years. Demand for contact lenses in blister packs has increased tremendously in recent years.

Further, analysts state that stringent rules and rising environment issues will lead to a decline in the usage of the plastic films during the forecast period.

Key Vendors:

• AEP industries

• Amcor

• Bemis

• Berry Plastics

• Jindal Poly Films

• Printpack

Other prominent vendors

• Allied Plastics

• ALPLA-Werke

• Ampac

• APPE

• Britton Group

• Charter Nex Films

• Daibochi Plastic

• DS Smith

• Exopack

• GP Plastics

• Graphic Packaging

• International Precision Components

• King Plastics

• Northeast Packaging Company

• Tegrant Alloyd Brands

Key market driver

• Growing demand for blister packaging in pharmaceutical industry

Key market challenge

• Environmental concerns

Key market trend

• High Demand for biodegradable plastic packaging films

1.3 Processes, Materials, Needs

Coextrusion is used in the following processes:

• Blown film

• Cast film (<10 mils or <250 μm)

• Cast sheet (>10 mils or >250 μm)

• Blow molding

• Tubing and sheathing

• Extrusion coating and laminating

• Profile

Fig. 1.3 is a coextrusion feedblock flow diagram where three extruders are employed to produce a three-layer asymmetrical structure. This particular design has the barrier on the outside with a tie layer to provide adhesion to the core resin.

Figure 1.3 Flow diagram of a coextrusion feed block where three extruders are employed to produce a three-layer asymmetrical structure.

While much polymer extrusion is done in monolithic form, coextruding polymers has been growing now for more than half a century. The polymer extrusion concept grew from the already existing technology for extruding processed foods ranging from cereals to meats. Likewise, coextrusion was practiced in the food industry, before it was practiced with molten polymers. Without realizing it, almost every reader has likely consumed some coextruded food in the form of candy, bakery item, cereals, or processed meats.

Some considerations as to why we may wish to coextrude polymers are:

• to bring desirable properties of different materials into one structure

• to reduce emissions from solvents used in adhesive lamination processes

• to process multiple materials in one pass into a structure to save process steps, cost, and time.

Coextruding polymers is no simple matter. In the food industry they have their compatibility issues, and in the polymer industry we take the complexity to a higher level. We must consider the three main scientific property arenas related to moving a polymer from solid form to liquid form, and back to differently shaped solid form, which are:

• thermal

• fluid

• mechanical [10].

Thermal considerations are important because the processes are nonisothermal. The science of fluid flow is important, because the fluids are non-Newtonian viscoelastic with nonlinear temperature-dependent viscosities. These fluids have interfacial boundaries that depend on the fluids’ viscosity and normal stress difference. Mechanical considerations are important, because the metal that contains the fluid flow is subjected to internal pressure forces, which distort the metal. The metal has to be shaped properly and has thermal mass and chemical resistance characteristics, which interact with the flowing fluids.

However, the benefits of combining materials in coextrusion far outweigh the challenges associated with such an endeavor. Coextrusion provides solutions to meet product functionality. There are many film properties that need to be taken into consideration when designing a packaging film. Some properties relate to the surface characteristics, while others relate to the entire thickness/body of the film. Surface characteristics include: coefficient of friction (COF), gloss, haze (surface induced), and sealability, as well as surface tension and chemical receptivity, which are important for materials to be printed. Body characteristics include: tensile properties, elongation, haze (internally induced), transparency, color, impact strength, and several other parameters.

Additionally, packaging requirements may also include gas and aroma barrier, chemical resistance, puncture resistance, formability, and shrink properties. In a world where energy prices keep rising, the biggest challenge is to have a structure that includes all the desirable properties in the most economical way. This requires that processors properly understand the material properties, as well as grasp polymer rheology to achieve an optimal formulation especially when attempting to coextrude [11].

In designing a coextruded film, one has to consider the fitness for use which translates into the following substitute quality characteristics:

• Physical properties

• tensile, elongation, flexure, stiffness,

• hardness, toughness, puncture, COF,

• sealability, peelability, etc.

• Barrier properties

• oxygen, moisture, oil, chemical,

• aroma/fragrance, carbon dioxide, etc.

• Additives

• colors, mineral fillers, COF modifiers, melt fracture inhibitors, scavengers, etc. [12]

Coextruded structures normally have a bulk layer, a barrier layer, a sealant layer, and often an adhesive layer to join incompatible layers. In some applications where using reclaimed materials are acceptable, the Reclaim also has to be considered. You can put it back into its own layer or as a combined blend into the bulk layer with virgin resin [13].

Common bulk layer choices are usually from the following groups [13]:

• PE (polyethylene)

• HD (high density), LLD (linear low density), LD (low density), VLD (very low density)

• PP (polypropylene)

• HoPP (homopolymer PP), CoPP (ethylene-propylene copolymer), Ter-PP (ethylene-propylene-butene terpolymer), and impact CoPP

• Acrylates

• EMA (ethylene methyl acrylate)

• EBA (ethylene butyl acrylate)

• EEA (ethylene ethyl acrylate)

• PMMA (poly(methyl methacrylate))

• EMMA (ethylene/methyl methacrylate)

• EVA (ethylene vinyl acetate)

• Low %, Mid %, High % VA

• PS (polystyrene)

• HIPS (high-impact PS), GPPS (general purpose PS)

Important criteria for consideration are:

• cost

• adhesion

• flexibility

• softness

• stiffness, etc.

Resin selection criteria are:

• melt index—MW & MWD (physical properties tensile strength, organoleptics)

• density—crystallinity (opticals, permeability, modulus—ie, LDPE)

• molecular branching—melt strength, processing parameters

• comonomer content—all properties

• melt point—crystallinity (seal initiation temperature—thermoforming).

Following are generic names for extrudable resins. When the polymer brand/grade is unknown, these names help communicate about the material [13].

• Polyethylenes

• HDPE—high-density polyethylene

• HMW-HDPE—high molecular weight HDPE

• MDPE—medium-density

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    Excellent technical books for flexible packaging applications, very helpful knowledgeable