1 Basics of Polymer

Packaging

„„1.1 Definition of Polymers
Polymers, commonly called plastics, are artificial products that are not available in
nature. They are produced artificially from basic organic materials, crude oil, natu-
ral gas, or even biomass. The initial products, so-called monomers, are low molecu-
lar weight gases or liquids. High molecular weight macromolecules with solid con-
sistency are synthesized through chain reactions and sometimes through
cross-linking. Also, inorganic elements are used to manufacture polymers like
PVC, where chlorine is used. There are, however, many examples in nature where
high molecular weight products are made through biosynthesis from low molecu-
lar weight substances in plants, animals, or insects. Examples are resins or rubber
in plants and carbohydrates, fats, or proteins in animals or insects.

„„1.2 Manufacturing of Polymer Resins

Low molecular weight monomers are produced through fractional distillation and
cracking of petroleum or natural gas. There are three different reactions in the
synthesis of plastics from the monomers: polymerization, polycondensation, and
polyaddition. In polymerization, the unsaturated double bonds of the monomers
are cracked and then the radicals polymerize in a random manner into high molec-
ular weight plastics. Examples are PE (Fig. 1.1), PP, and PVC (see abbreviations list
on pages XV–XVII). Polyaddition polymerization can take place in an autoclave ei-
ther at low or high pressure or in a tubular reactor. In polycondensation, the mono-
mers react with each other through the loss of one low molecular weight product
like water and create high molecular weight plastics through a chain reaction. Ex-
amples are PA and PET. Finally, in polyaddition, the molecular structure of the
monomers is rearranged and linked with each other through cross-linking to high
2 1 Basics of Polymer Packaging

molecular weight plastics. A typical characteristic of cross-linking is that it is a

chemical bonding through the main valency and is not a physical bonding like van
der Waals forces or hydrogen bonding, which has an ionic nature. Polyurethane is
an example of this type of plastic (see Fig. 1.2). Macromolecules of the first two
types have a linear structure with some side branches, but the characteristic of
polyurethanes is a typical cross-linking structure. Also, elastomers (rubbers) have
cross-linking structures.

Polyethylene

—[ CH2 —— CH2 —
] n
E
E E
H H H H H H H H H H

C C + C C C C + C C + C C

H H H H H H H H H H ………

E
H H H H H H H H

C C C C C C C C

H H H H H H H H ………

E = Energy in the form of heat, γ-rays, UV rays, and catalysts or peroxide radicals

Figure 1.1 Polymerization of polyethylene (PE)

Amorphous Semicrystalline
Thermoset Plastics Thermoplastics Rubber/ Elastomer

Figure 1.2 Molecular structure of different polymers

 1.3 Classification of Plastics: Molecular Structure 3

„„1.3 Classification of Plastics:
Molecular Structure
Looking at molecular structures, plastics are classified into three groups:
1. Thermoplastic polymers
2. Thermoset polymers
3. Elastomers
Thermoplastics have a linear structure with no or a very low level of branching and
can go through repeated melting and solidification cycles. During heating, the
Brownian movement of the macromolecules increases, resulting in a reduction of
stiffness. At elevated temperature they are so soft that they can be deformed with
low force. At higher temperatures they ultimately melt and can be extruded for
different production processes.
There are two types of thermoplastics. In the first type, the macromolecules build
a random cluster. Different chain segments have hydrogen-bridge bonding when
they come close to one another. Through this phenomenon they have a stiff struc-
ture. Moreover, they form an inhomogeneous molecular structure. They are called
amorphous thermoplastics. Examples are polystyrene (PS) or polyvinylchloride
(PVC). They are transparent. The transparency can be enhanced through molecu-
lar orientation during manufacture.
In the second type, the macromolecule chains are partly arranged as amorphous
structures and partly in a parallel structure like a packet, the so-called crystallites.
These crystallites arise through high physical bonding between the chain seg-
ments, which run parallel to one another. Besides chain packets, other geometrical
structures like spherulites are also possible. The molecular structures of crystal-
lites are so congested that light can pass only partially through these structures.
These types of thermoplastics are called semicrystalline polymers. Examples are
polyethylene (PE), polypropylene (PP), or nylon (PA). Semicrystalline polymers
with a high amount of crystallites are opaque, for example HDPE (high density
polyethylene). Due to their inhomogeneous structure, semicrystalline polymers
show inhomogeneous characteristics during thermoforming. Amorphous thermo-
plastics are much stiffer than semicrystalline plastics. The level of crystallinity in
a semicrystalline plastic will determine the melting temperature. A highly crystal-
line polymer such as HDPE, PA, and often PTFE (with very high crystallinity) will
have a higher melting temperature than a less crystalline polymer such as LDPE.
4 1 Basics of Polymer Packaging

Here are a few examples:

HDPE: 130°C; LLDPE: 110°C; Ionomers: 90°C; PP: 165°C; PET: 250°C;
PA-12: 175°C; PA 6 12: 215°C; PA-6: 220°C; PA-66: 254°C
The macromolecules of elastomers are cross-linked, but the knots of cross-linking
are widespread. A typical characteristic is their low stiffness (elasticity), but be-
cause of cross-linking they are unable to melt. At elevated temperatures a thermal
destruction takes place, but they are still unable to melt.
Thermoset plastics (duroplastics) have a structure similar to elastomers, but the
cross-linking is by far more congested. The macromolecules are completely unable
to move and show almost no Brownian motion. They are very stiff and brittle. Like
elastomers (rubber), here also a thermal destruction takes place at elevated tem-
peratures, for example in Araldite. Usually the monomers are low molecular weight
liquids that react to form a thermoset network that is irrevocably cross-linked and
does not allow any thermoplastic deformation thereafter.
Thermoplastics are the only polymers that are used to make polymer packaging.
Elastomers and duroplastics are used only occasionally as a supporting material.

„„1.4 Plastics Additives
The plastics to make packaging materials are supplied as granules (resins) or pow-
der. Although they could be extruded to different products like film or other pack-
aging materials, they do not fulfill the different requirements that packaging
should possess, or sometimes the production speed or machinability of a film is
poor. In order to achieve an optimal characteristic, the plastic resins are mixed
with additives. These are auxiliary substances for plastic resins that will optimize
different characteristics. The most common terms used in the processing of addi-
tives are next:

Compounding
Resins are mixed with a very low amount (∼1%) of additives. A twin screw extruder
(TSE) or sometimes a planetary extruder (for PVC manufacturing) is necessary to
mix the components homogeneously.

Blend
Two or three different resins (not additives) are mixed at different ratios in a single
screw extruder (SSE) ideally equipped with a mixing head or even a twin screw
extruder. The goal is to get better properties in the packaging material.
 1.4 Plastics Additives 5

Masterbatch
When a virgin resin is mixed with a compound, which is mostly the same resin
with some particular additive, then this compound is called the masterbatch. The
amount of compound could be 5–10%.
Blends are made with resins of similar granule sizes and densities, so that’s why it
can be processed by a single screw extruder. The manufacturing of the master-
batch and the compounding of different components with different granule sizes
and densities or powder, pastes, and sometimes even liquids (slip agent) are done
with twin screw extruders. In twin screw extruders the grade of mixing is high,
and hence the resins made are homogeneous.

1.4.1 Usual Additives in the Packaging Sector

1.4.1.1 Antioxidants
Through the presence of residual monomers, dirt, or residuals of catalysts, oxida-
tion takes place in a resin with the presence of oxygen. Heat and light catalyze this
process. Chain scission of the polymer produces radicals that cause further degra-
dation of the polymer. This type of reaction is called autoxidation. The polymer
loses its brightness and stiffness and ultimately ages. The chain scission of a linear
polymer with 10,000 monomer units and a contamination level of 100 ppm is suf-
ficient to halve the molecular weight of the polymer. Antioxidants like aromatic
amines or phenols scavenge the radicals, hinder degradation, and stabilize the
polymer, particularly in outdoor use.

1.4.1.2 Light Stabilizer
Light, particularly the ultraviolet spectrum, also induces degradation in polymers,
deteriorating the optical and mechanical properties. In particular, polymers con-
taining impurities or chromophores are more sensitive to light. Not all polymers
are similarly sensitive; PE is more resistant to light than PP. The stabilizers are
mostly HALS (hindered amine light stabilizer) of different structures.

1.4.1.3 PVC Stabilizer
PVC, when processed at high temperature, loses hydrochloric acid (HCl), which
scissions the macromolecules and causes cross-linking. This results in discolor-
ation and changes the physical and chemical properties. Stabilizers are mostly car-
boxylated metals like K, Ca, or Ba, which scavenge HCl. Other stabilizers are alkyl
phosphites and fatty acid esters.
6 1 Basics of Polymer Packaging

1.4.1.4 Antiblock Agents
Thin films tend to stick together through surface forces, which cause blocking of a
roll during unrolling. The film unrolls inhomogeneously, and it can even tear. Anti-
block agents are made of inorganic particles that keep some distance between the
film layers, enabling air to get in between them. The film can then be unrolled
smoothly. Typical antiblocking agents are silica, talc, or limestone.

1.4.1.5 Antifog Agents
Moist food packed at ambient temperature when cooled creates fog through con-
densation of water vapor. The humidity deposits on the bottom side of the top film
and makes it hazy. Because of the high difference in surface tension between poly-
olefin films and water droplets, there is no homogeneous layer of water on the film.
In order to gain a clear view into the pack, antifogging agents (AFAs) are extruded
in the film. The antifogging agents migrate to the film surface and reduce the sur-
face tension of water droplets, creating a homogeneous water layer. The view is
then clear. Typical AFAs are glycerol or sorbitan esters.

1.4.1.6 Nucleating Agents
In order to increase the speed of crystallization in semicrystalline polymers such
as HDPE, PP or PA (nylon), and polyesters, in particular, nucleating agents are
added. The mechanical strength of the film increases, so a thinner film can
be produced. This procedure is used for high-speed production or to produce
thinner films of expensive resins like nylon. The nucleating agents are generally
resins of a higher melting point (butane) or inorganic salts of alkali metals
(sodium-2-chlorobenoate).

1.4.1.7 Lubricants as Processing Aids

Lubricants are polymer processing aids that enable smooth production of the poly-
mer melt without tearing the melt flow or producing a melt flow surface like shark
skin. Also, the production speed is increased. These are mostly hydrocarbon waxes,
fluoroelastomers, fluoropolymers, or silicone-based additives. These are extruded
first to get a layer on the inner wall before the main resin is extruded. This retards
the adhesion of burned particles on the inner wall of the barrel.

1.4.1.8 Slip Agents
Slip agents reduce the coefficient of friction (COF) of a film during its machining. It
is particularly important for films in high-speed packaging lines, as in a vertical-
form-fill-seal machine (VFFS). The agents are mixed with the resin and are not com-
 1.4 Plastics Additives 7

patible with the resin. After production, they migrate to the film surface and behave
as a surface lubricant. Two very well-known slip agents are erucamide and oleamide.

1.4.1.9 Antistatic Agents
Polymers, particularly nonpolar polyolefins, are bad conductors of electricity, and
hence, polymer products generate very high electrical charges locally through fric-
tion. This can cause an unwanted discharge of electrical current and dust absorp-
tion from the air, particularly when the air is dry. Antistatic agents are of two
types, external and internal. External agents are sprayed or coated on the surface,
like in tubes. They can act at once but may get lost through abrasion. The internal
agents behave like the slip agents—they are nonsoluble in the polymer matrix and
migrate to the surface. They are used to absorb water vapor and make the polymer
surface able to conduct electricity. The local charge can be distributed or can be
removed from the film surface. Examples are fatty acid esters or alkyl phosphates.
There are also permanent, nonmigrating antistatic agents, which essentially are
polymers that form a second phase in the matrix polymer film in the form of a
more or less continuous network, and in this way, create antistatic properties. In
this case, no migration will take place, and the antistatic properties will be imme-
diately effective and be permanent over time.

1.4.1.10 Colorants
Colorants give a polymer matrix a particular color. There are two types of colo-
rants. Dyes are soluble in a polymer matrix and give a transparent look. Pigments,
on the other hand, are insoluble. If the pigments have a size smaller than 0.2 μm,
then visible light can pass through the polymer and it will appear transparent. If
the particles are bigger than 0.2 μm, then light cannot pass and the polymer ma-
trix appears opaque. The dyes are of organic origin. Pigments are inorganic mate-
rials, mostly oxides like TiO2 or Fe3O4.

1.4.1.11 Optical Brighteners
White-colored polymers and also transparent polymer films often degrade under
low-wavelength light, in particular UV rays. A white-colored polymer changes to
yellowish as the absorption spectrum of the material changes. This phenomenon is
also known in white textiles, paper, lacquers, or dyes. Color wavelengths in the
region of violet, indigo, and blue are absorbed more, so the intensity of the yellow
color increases. The polymer materials look dull. In order to get a brightening ef-
fect, blue–color–additives are used to compensate for the lost wavelengths. These
possess a fluorescing effect.
8 1 Basics of Polymer Packaging

1.4.1.12 Chemical Blowing Agents

These are mostly organic chemical agents that when heated evolve gases. The
gases increase the volume of a polymer, thus reducing the mass and the cost. Fur-
thermore, their foam structure gives a particular touch effect (soft touch effect) and
is interesting for marketing. Through the foamed structure the layer diffracts light
and appears white, which reduces or saves on white printing ink. This also reduces
the cost of garbage in countries like Germany. These may be carbonates, azo com-
pounds, semicarbazides, or similar products. A sound knowledge of chemistry is
advantageous in working with these agents.

1.4.1.13 Antimicrobial Agents
In order to kill microorganisms or at least stop their growth, antimicrobial agents
can be used in polymer films. There are different killing systems: some inhibit the
metabolism of microorganisms through contact, some dehydrate them, and so on.
If the agent is heat stable, then it can be extruded. If not, then coating with a lower
drying temperature is the better way. Some agents could also be sprayed. Silver
metal, quaternary ammonium compounds, or N-halamine-based antimicrobial ad-
ditives are known.
For all types of additives, the legislative aspects for food, cosmetic, and other appli-
cations must be considered.

„„1.5 Required Performance of
Polymer Packaging
Plastic packaging must fulfill a number of requirements or performance properties
in order to be used as primary packaging. They are mainly the mechanical proper-
ties, the barrier properties, the sealing properties, and sufficient chemical resis-
tance (ESCR) against the environment and also against the product packed in it.
The mechanical properties are the tensile strength, puncture resistance, tearing
strength, stiffness, and so on. Barrier properties mean low permeation by light,
oxygen, moisture, CO2, aroma, or fat. Every packaging material must be properly
sealed so that the seal strength and also the sealing integrity are sufficient high for
the expected shelf life and mode of handling of the package. Finally, the chemical
resistance guarantees the integrity of the whole package for the shelf life. Migra-
tion of product components into the packaging material or vice versa must be re-
duced to a minimum so that stress cracking or damage of the packaging material
or auxiliary parts like printing ink, lacquer, or adhesives either does not arise at all
 1.6 Different Types of Polymers Used for Packaging 9

or is kept to a minimum during its shelf life. Not only the legislative requirements
but also the responsibility of a producer to its customers must be fulfilled.

„„1.6 Different Types of Polymers

Used for Packaging
To fulfill different requirements for a packaging application, different polymers are
used. In the following chapter the usual polymers employed in packaging are dis-
cussed. These can be divided into three groups: structural polymers, which are
used to make the body of the packaging; functional polymers, which are used in a
lesser amount but to achieve particular properties, mostly high barrier properties
and for environmental stress crack resistance (ESCR); and special polymers that
are used in a much lesser amount to achieve very sophisticated properties, such as
tie or adhesive layers, blends for good sealing, blends for peel sealing, or special
touch effects.

Group 1: Structural Polymers

These groups of polymers are used to make the packaging body.
PE Polyethylene
LDPE Low density PE
MDPE Medium density PE
HDPE High density PE
LLDPE Linear low density PE
EVA Ethylene–vinylacetate

PP Polypropylene
ƒƒ Homopolymer
ƒƒBlock copolymer
ƒƒRandom copolymer
ƒƒGraft copolymer
ƒƒBOPP: biaxially oriented flexible PP

PS Polystyrene
HIPS High impact polystyrene
OPS Monoaxially oriented polystyrene
10 1 Basics of Polymer Packaging

PET Polyester
PET-A Amorphous polyester
PET-C Crystalline polyester
PET-G Glycol modified polyester (cyclohexane dimethanol)
BOPET Biaxially oriented flexible PET

PA-6 Polyamide / nylon

OPA / BOPA (ONy / BONy) mono- or biaxially oriented nylon
PVC Polyvinylchloride

PLA Polylactic acid

OPLA Mono- or biaxially oriented polylactic acid copolymers

Group 2: Functional Polymers

These groups of polymers offer functional effects like a high or very high barrier to
oxygen, moisture, CO2, aroma, or fat. Some offer high puncture resistance.
EVOH 
Ethylene–vinyl alco- High barrier against gases, aromas
hol-copolymer
PVdC 
Polyvinylidene chloride High barrier against gases, moisture,
aromas
MXD6 
meta-xylene diamine High barrier against gases, moisture,
aromas
Amorphous PA High barrier against gases, moisture, aromas,
as additive to PA-6
PVOH 
Polyvinyl alcohol High barrier against gases
PEN 
Polyethylene naphthalate Better barrier against gases
COC 
Cycloolefin copolymer Performance polymer
PAN 
Polyacrylonitrile Properties similar to PVC, but a lesser
amount
PA-6 
Polyamide/nylon For better puncture resistance
Ionomers 
For oil fat resistance, high hot tack, low seal initiation temperature,
high stiffness, and high puncture resistance (although lower than PA)
 1.6 Different Types of Polymers Used for Packaging 11

Group 3: Special Polymers

These groups of polymers offer special effects, like providing very good sealing or
adhesion performance (for example, EMA to PET, EMAA to aluminum foil, and so on).
mLLDPE Metallocene LLDPE
ULDPE Ultra low density PE
VLDPE Very low density PE

EVA Ethylene–vinyl acetate copolymer

EAA Ethylene–acrylic acid copolymer
EMAA Ethylene–methacrylic acid copolymer
EBA Ethylene–butyl acrylate copolymer
EMA Ethylene–methyl acrylate copolymer
Ionomers Metal ion modified EAA or EMA

1.6.1 Polyurethanes as Adhesives

Modified polymers or polymer compounds like maleic acid anhydride are used as
tie layers during coextrusion. Elastomers or modified elastomers are used as plas-
ticizers for a soft touch.
Different polymers show different properties regarding their barrier characteris-
tics. A perfect packaging material is always a combination of different polymers or
of polymers with paper or metal. Mostly aluminum is used to make composites,
because it is a soft metal, is easy to convert, and fulfills almost all requirements to
make a very high barrier film or sheet. Because aluminum is not resistant against
a number of chemicals that are present in a lot of foods or other products, it is
coated with a suitable lacquer. Paper is used to increase the stiffness of packaging
and also as a very good printing substrate.
12 1 Basics of Polymer Packaging

„„1.7 Short Description of Some Polymers for

Packaging Applications
PE PE or polyethylene is the most common polymer for packaging purposes.
Based on the density and molecular structure, a number of PEs or modified PEs are
used.
LDPE Low density PE is polymerized from the gaseous monomer ethylene at
high pressure. The molecular structure is highly branched. The molecular volume
is relatively high, and the density is low, generally between 0.910 to 0.940 g/cc. Its
melting point (melting region) is around 100°C. Because of the low melting point,
it is used as a sealing polymer. Moreover it is neutral against different food, cos-
metics, and chemicals. It offers a good barrier against moisture but less against
oxygen. LDPE is generally used as a sealing layer, as a blend in collapsible tubes or
pouches.
MDPE MDPE is not an official abbreviation but it is used by the polymer technol-
ogists to mean a PE in the density range around 0.94 g/cc produced at low pres-
sure using a Ziegler–Natta (ZN) catalyst system. The physical properties are simi-
lar to LDPE or HDPE. It has a lower sealing temperature than HDPE, and its
organoleptic property is pretty good. An MDPE sealing layer is often neutral against
delicate foods like water or fresh milk.
HDPE The macromolecules are almost branchless, linear, and show higher den-
sity and are produced at high pressure, generally more than 0.950 g/cc. Because of
the high linearity, the amount of crystallites in HDPE is much higher than in
LDPE, it can be up to 80%. HDPE has a much higher tensile strength and stiffness
than LDPE. Its melting point is 130°C. HDPE pouches can also be used for moder-
ate retorting purposes. HDPE has a high moisture barrier and is generally used as
caps, bottles, carrying bags, heavy-duty sacks, or as a blend in collapsible tubes.
LLDPE It is usually a copolymer of ethylene and butane, hexane, or octane pro-
duced with a ZN (Ziegler-Natta) catalyst system at low pressure. Ethylene makes
the main chain; the other monomers make side chains like a comb. LLDPE has a
higher melting point than LDPE and can also be used for partial retorting pur-
poses. The melting point is approximately 120°C. It offers better sealing strength
than LDPE. Also, it is used as a blend with LDPE or HDPE for fine tuning of differ-
ent structures or as a sealing layer.
mLLDPE The letter “m” means metallocene. The distribution of polymer molecu-
lar weight in a metallocene variation is pretty narrow because of special catalysts
containing the metallocene configuration, in comparison to polymers that are po-
lymerized through a standard procedure using Ziegler-Natta (ZN) catalysts. Films
made of such a polymer show higher transparency than standard ethylene copoly-
 1.7 Short Description of Some Polymers for Packaging Applications 13

mers despite a composition similar to conventional LLDPE or HDPE. Their sealing

window is also narrow because of the narrow distribution of molecular weight.
Therefore trouble in sealing seams may arise if the temperature distribution at a
sealing jaw is broad, particularly in old packaging machines.
PE Copolymers PE has a number of copolymers, particularly acid copolymers, to
achieve special properties.
EVA It is a copolymer of ethylene and vinyl acetate (VAC). The softness, transpar-
ency, and elasticity of a film increases with a higher content of VAC. The comono-
mers reduce the crystalline percentage in a polymer. Also, the sealing integrity of
EVA is higher than LDPE when fatty foods are packed. However, the VAC content is
kept generally below 6.5% for food packaging because an acidic odor is perceptible
if the VAC content is higher. In particular, if films or pouches made of EVA are to be
upgraded with the use of beta radiation, then the odor may be disturbing although
not unhealthy.
EMA EMA is a polymer similar to EVA, but ethylene is copolymerized with methyl
acrylate instead of with vinyl acetate. Advantages over EVA copolymers are the
higher heat resistance (thermal stability of more than 300°C versus 220°C for EVA
copolymers) and the superior adhesion to PET substrates in cases where these
polymers are made on a tubular reactor.
EAA/EMAA The comonomer here is acrylic acid or a methyl ester of it. This is
highly tacky and is used, depending on the target, as a sealing layer or as a tie
layer. The acrylic acid content in EAA or EMAA is generally 5 to 15% for Al compos-
ites.
Ionomer This polymer is created when EMAA is partially neutralized with NaOH
or other base (e.g., Zn). Because there are almost no crystallites left or because
they are extremely small (<100 nm), this is highly transparent. It can be very
tough, and some modifications are used as a fat-resistant sealing layer with high
hot tack. Because of the cross-linking introduced by the metal ions, it also has ex-
cellent thermoforming, stiffness, hot tack, and shrink performance and is used for
example in shrink bags for meat packaging.
PP Propylene gas is the monomer of PP. This a semicrystalline polymer with a
melting point at 160°C (homo-polypropylene). Based on the position of the CH3
side group, there are three different types of PP: isotactic, atactic, and syndiotactic.
The crystalline content is different in the different types. It is stiffer than PE and
can be used for retort applications because of its higher melting point. It has versa-
tile applications. Filled PP can be thermoformed to containers whether transparent
or filled with suitable additives. After biaxial stretching it is called BOPP, and is
used widely as a good printing substrate for flexible packaging. It is a very good
moisture barrier but a poor oxygen barrier. If necessary, the smooth surface of
BOPP is deposited with Al, SiOx, or AlOx to achieve a high oxygen barrier.
14 1 Basics of Polymer Packaging

Random-PP This is a copolymer of propylene with ethylene, where the ethylene

clusters are distributed in a random manner—hence the name random-PP. The eth-
ylene content is generally around 5%. This is softer than homo-PP.
Block-PP This is a copolymer of propylene with ethylene, where the ethylene
clusters are distributed in blocks—hence the name block-PP. The ethylene content
is generally around 5%. Transparency is higher, and the elasticity at low tempera-
ture is higher than that of other PP types. It is suitable for deep-frozen food pack-
ages, which could be heated in a microwave.
PA Polyamide or nylon is a semicrystalline polymer, and mostly the PA-6 or PA-6-
type copolymers are used for packaging purposes. Nylon has a very good oxygen
barrier property and high puncture resistance. For packing meat or meat products,
fish, or different medical products, a composite like PA/PE, eventually with a high
barrier layer of PVdC or EVOH, is the best solution. PA-6 is a polycondensate of
ε-caprolactam. Other polyamides used for special packaging purposes are PA-66
and PA-12. PA-66 is a condensation product of hexamethylenediamine and adipic
acid. The monomer of PA-12 is laurolactam. Laurolactam is tough and has a high
dimensional stability. It is used as a blend with other PAs to extrude multilayer
composites for thermoforming or blow molding. Amorphous PA freezes out of the
melt without crystallites. It has higher stiffness and transparency than the other
types. Economical use is only possible with shrink films. PA films are also oriented
monoaxially or biaxially to make dimension-fixed film with higher mechanical
properties and a highly smooth surface suitable for high-quality printing or depo-
sition of Al, SiOx, or AlOx for a very high barrier.
Amorphous PA usually has excellent oxygen barrier properties, in particular at
high humidity levels, and can be used to reduce the severity of retort shock. In ad-
dition, it can be used to modify EVOH for better thermoformability.
PET Although called polyester, we understand that PET is almost always polyeth-
ylene terephthalate, which is a condensation product of terephthalic acid and eth-
ylene glycol. It is a semicrystalline polymer. Although both nylon and PET split a
molecule of H2O during polycondensation, PET is much more sensitive to H2O
during extrusion than is nylon. Other than nylon, PET resin has to be dried prop-
erly before extrusion. Otherwise water vapor in the melt creates acetaldehyde
through hydrolysis, which has a pungent odor, making it unsuitable for packing
foodstuffs. PET has different variations:
PET-A is an amorphous variation of PET and is extruded as a sheet to be thermo-
formed into containers. It is also injection molded to test-tube-like preforms to be
stretch-blow-molded in a second step to bottles.
PET-C containers are thermoformed from a  PET-A sheet and then crystallized
after thermoforming to PET-C. These containers are very hard and dual ovenable,
meaning both in microwaves and baking ovens.
 1.7 Short Description of Some Polymers for Packaging Applications 15

PET-G is a glycol-modified variety of PET that is amorphous and highly transpar-

ent. This is both injection molded and extruded to sheets. The alcohol part, gly-
col, is replaced partially by cyclohexane dimethanol. Oriented PET-G films are
also used for label manufacturing.
BOPET is the biaxially oriented variation of PET, which is highly dimensionally
stable. It is the best polymer substrate for printing, and it is used for high-quality
packaging, particularly for retort packing.
PVC-U PVC-U (unplasticized) is an amorphous polymer and is polymerized from
vinyl chloride. PVC is a sensitive polymer: it degrades under heat. Extrusion of
PVC needs a number of additives like a  stabilizer, optical modifier, and Cl2 ab-
sorber beforehand. Extrusion is complicated and takes place in multiple steps. PVC
has versatile uses, like sheets for thermoforming as food containers and pharma-
ceutical blisters. Because it is an amorphous polymer, it can be thermoformed eas-
ily with a very good wall thickness distribution. Bottles are seldom made. It is used
in monoaxially oriented form as shrink labels. PVC can be modified with plasticiz-
ers like citric acid derivatives or phthalates to form soft PVC, which is used as a
stretch film for wrapping purposes.
PS Polystyrene is an amorphous polymer and is polymerized from the monomer
styrene. For packaging applications mostly homopolymer is used. It is highly trans-
parent, glossy, and brittle. For thermoforming applications, it is grafted with plas-
ticizer to enhance the impact properties. This is called HIPS: high impact polysty-
rene. It can be thermoformed easily like PVC-U in a broader temperature window
than semicrystallines like PP and is used for thermoformed containers or cups.
Also, as an oriented film, it is used for labels. PS is a cheap thermoplastic and is
used in vast amounts as sheet with or without high barrier sheets with EVOH.
PVdC PVdC is very sensitive polymer. The dispersion grade for coating is usually
copolymerized with vinyl chloride. The extrusion grade is copolymerized with eth-
ylene for higher thermal stability. It is a unique polymer with a very high barrier
against oxygen, moisture, and aroma. Particularly for pharmaceutical packaging,
the PVC-U sheets are coated with a PVdC dispersion.
EVOH EVOH is a copolymer of ethylene and vinyl alcohol. The vinyl alcohol part
is brittle and offers very high oxygen and aroma barrier properties. The ethylene
component offers flexibility. The higher the vinyl alcohol content, the higher the
barrier effect but also with brittleness and poorer thermoformability in multilayer
rigid packaging structures. A high vinyl alcohol grade with less ethylene (27 mol%)
offers indeed a high barrier, but it is not suitable for flexible packs like collapsible
tubes or thermoforming applications. These types can be used as the top film on
containers. Grades like 38 mol% or 44 mol% ethylene are suitable for thermoform-
ing or for collapsible tubes. Another problem of EVOH is its sensitivity to moisture.
Particularly during retorting at high temperature under water vapor, the EVOH
16 1 Basics of Polymer Packaging

layer in a composite gets wet and loses its high barrier property against oxygen. It
takes weeks to recover the barrier property.
In order to overcome these shortcomings, EVOH suppliers are continuously devel-
oping modified grades to improve the thermoformability. Also, amorphous polyam-
ides or ionomers can be used for this purpose.

„„1.8 Major Polymers Used in Packaging

Table 1.1 Polymer Attributes and Applications

Polymer Key Attributes Applications

LDPE Transparency, sealability Flexible food and pharma packaging
LLDPE Puncture resistance, ESCR, hot tack Laminates, rotomolded containers
HDPE High strength & toughness Laminates, woven sacks, blow-molded
containers, crates, caps
PP Chemical resistance, hot fillable, steril- Laminates, woven sacks, blow- and
izable, good impact & clarity, hinge injection-molded containers, caps
PET Gas barrier, clarity Laminates, bottles
Nylon Gas barrier, oil resistant, impact Multilayer flexible and rigid package
EVA ESCR, toughness Multilayer flexible and rigid package
PVC Clarity, extremely versatile Blister packaging, films
Styrenics Stiffness, expandable Thermoformed trays & containers
Source: Raj Datta, Haldia Petrochemicals, National Conference, IIP, Kolkata 2012

1.8.1 Important Points for the Technologist

1. In order to manufacture a tailor-made polymer packaging material for a particu-

lar application, the proper resin has to be found. Generally, the sealing layer is
decisive for products like food or cosmetics that contain fat, spices, or other
components that may be corrosive for this layer. The pack must function through
the shelf life. Proper resin, for example, LDPE-grade, from a particular supplier
helps a lot. Some other LDPE types are not suitable. In most cases a correct
blend will help. It is a question of patience and also a matter of luck how quickly
the proper solution can be found. Experienced specialists at the resin manufac-
turers and also additive suppliers are good resources.
 References 17

2. Critical trials with new specifications should not be made on a production ex-
truder, particularly with new additives. Preliminary trials should be done ei-
ther on a trial extruder in one’s own company or at an extruder of some univer-
sity or institute or at the resin or additive supplier. Otherwise there is a risk
that the production extruder will have to be cleaned, which could take days.
Only the final trials should be done on the production extruder or line to be
sure that the specification will function or at least will not cause a big problem
with the extruder.
3. One should have a confidential relationship with a supplier before one discloses
the specification or even a part of the specification to a supplier. Even tempera-
ture adjustment at the extruder may give a specialist key knowledge on the
probable resin.

„„References
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Stuttgarter Verpackungstage (Stuttgart Packaging Symposium), (1997)
Schoene Werner, BASF, Polypropylen für Hartverpackungen, 4th Stuttgarter Verpackungstage (Stuttgart
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Verpackungstage (Stuttgart Packaging Symposium), (2001)
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12th Stuttgarter Verpackungstage (Stuttgart Packaging Symposium), (2005)
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packungstage (Stuttgart Packaging Symposium), (2012)
Volk Aschulmann,  Einsatz von Additiven bei Verpackungsfolien, 18th Stuttgarter Verpackungstage
(Stuttgart Packaging Symposium), (2011)
Hausmann Karl-Heinz, DuPont, Personal Information
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Stuttgarter Verpackungstage (Stuttgart Packaging Symposium), (2012)
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packungstage (Stuttgart Packaging Symposium), (2008)
Hutter Matthias, Solvin, PVdC - ein bewährtes, universelles Barrierematerial mit Innovationspotential,
15th Stuttgarter Verpackungstage (Stuttgart Packaging Symposium), (2008)
18 1 Basics of Polymer Packaging

Schambony Simon, BASF, UV-Schutz in transparenten Verpackungen, 15th Stuttgarter Verpackungstage

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