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Laminating Adhesives for Flexible Packaging

by Edward M. Petrie

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1. Introduction
2. Wet and Dry Lamination
3. Substrate Characteristics
4. The Laminating Adhesive

The variety of modern flexible packaging products that are available today would not be
possible without modern adhesive systems. The evolution of the packaging industry has
closely matched the development of new adhesive materials and production processes. These
trends have led to high quality and technically demanding packaging structures required by
the consumer.

For many applications in flexible packaging, the use of a single material may not satisfy all of
the properties demanded of the product. In these cases, a composite consisting of two or more
layers of material may provide the desired performance. A particularly common means of
creating such a composite is to laminate various polymeric films to other films, foils, papers,
etc. with a polymeric adhesive.

This production solution is commonly employed in the packaging industry where the end-
products require multi-functional properties, such as high tensile strength and high gas
permeability. These are generally referred to as barrier films. The laminate construction can
become rather complicated due to the nature of the specific application. A typical laminate
used in the medical packaging industry, for example, may be a multi-layer composite
containing films of polyester / polyethylene / metal foil / polyethylene.

Laminating adhesives for flexible packaging are available in a variety of technologies,

viscosities, and solids concentrations. There are four basic categories of laminating adhesive
that are commonly used. These are:

waterborne,
solvent based,
reactive 100% solid (solventless) liquid, and
hot melt.
Each category has a number of applicable base polymers and a wide variety of formulation
possibilities. The specific formulations will heavily depend on the nature of the laminating
process employed, the nature of the film substrate, and the final physical properties desired.

This article will provide a primer on laminating adhesives and processes used mainly for
flexible packaging. Thicker laminates (e.g., decorative laminates, wood laminates) can be
produced by bonding substrates in a hot press. However, these adhesives are outside the scope
of this article. The principles of the wet and dry laminating processes will be discussed first,
followed by a general discussion of the main adhesive systems that are usually employed.

2. Wet and Dry Lamination

The manufacture of film laminates is a relatively simple continuous process of coating and
bonding. Generic illustrations of typical flexible laminate production lines are shown in
Figure 1. Specific processes differ primarily by how the adhesive is applied and converted
from a liquid to a solid. There are several laminating processes that can be easily adapted to
production. These are generally classified as either wet or dry laminating processes and they
are described in Table 1.
 Figure 1: Relative peel strength of an acrylic latex
adhesive that is unmodified and modified with
tackifier.

Typical
Process Description Application Typical Adhesives
Equipment
Dry Processes
Polyurethane
A liquid adhesive is
dispersions, acrylic,
coated on a substrate,
emulsions, acrylic
dried with heat and air Gravure
Dry bond solvent, water-based
flow, and then application
laminating polyvinyl alcohol,
laminated to a second cylinder
ethylene vinyl
substrate via a heated
acetate copolymers,
compression nip.
silicone solvent
Low viscosity hot melt Heated roto- Ethylene vinyl
Hot melt
adhesives are applied gravure acetate, modified
seal
to substrate and then cylinder, polyolefins,
coating
later extruder polyesters
A liquid adhesive is
applied, dried with
heat and air, and then
Synthetic rubber,
bonded only with Same are dry
Cold seal acrylic / natural
slight pressure bonding
rubber
(formulated so that
tack to non-cold seal
surfaces is minimized)
Wet Processes
Liquid adhesive is Gravure Polyurethane
Wet bond
applied to a substrate, cylinder or dispersions, acrylic,
laminating
then immediately smooth roll emulsions, water-
 laminated to a second based polyvinyl
substrate via a nip alcohol, ethylene
followed by drying vinyl acetate
with heat and air flow copolymers
(one substrate must be
porous to allow
evaporation of water or
solvent)
The adhesive is
metered onto the
Multiple
Solventless substrata in liquid Polyurethanes,
application roll
laminating form. It is then mated polyesters
configurations
to a second substrate
via a heated nip
Table 1: Flexible Packaging Adhesive Bonding Processes

The main items in a lamination line are the film unwinders and winders, adhesive coater, and
laminator. There are a number of coating methods that can be used depending on the nature of
the adhesive. Specific applications may require varying degrees of adhesive coating thickness.
Table 2 shows a summary of some of the capabilities and limitations of common coating
methods that are used in producing laminates.

Type of
Coating Coating Coating
Coating Viscosity, Adhesives
Weight, Accuracy, Speed,
Method cps Commonly
gm/m2 +/- % m/min
Used
Solution,
Wire rod 100-1,000 15-100 10 100-200
emulsion
Solution,
Knife over 4,000-
25-750 10 100-150 emulsion,
roll 50,000
100% solids
Reverse 300- Solution,
25-250 5 100-400
roll 50,000 emulsion
Solution,
Gravure 15-1500 2-50 2 100-700
emulsion
Emulsion, hot
Extrusion 400-
15-750 5 300-700 melt, 100%
die 500,000
solids
Emulsion, hot
400-
Slot die 20-700 2 100-300 melt, 100%
200,000
solids
50,000- Emulsion, hot
20-500 2 100-500
Curtain 125,000 melt
Table 2: Summary of Capabilities / Limitations of Common Coating Methods 2

With either wet or dry laminating, full bond strength generally occurs over about a period of
24 hours. Therefore, initial tack or "green strength" is often an important criterion for a
laminating adhesive. The immediate bond strength must be sufficient to hold the substrates
together and resist relaxation of the web until higher bond strengths can be achieved. Various
technologies have been developed to either speed the strength development or to provide
improved properties in laminated products. These include the application of UV or electron
beam for crosslinking and the addition of chemical crosslinking agents in the adhesive
formulation.

Wet Laminating
With wet laminations, the adhesive is applied to one substrate, usually by roller coating or air
knife. The coated substrate is then nipped with another substrate, and the resulting laminate
may then be left to air dry or passed through a heated oven to remove solvent and build bond
strength. The types of adhesive used for wet lamination are:

waterborne natural products, such as starch and dextrin or

waterborne synthetic latex products, such as polyvinyl acetate, acrylic, etc.
100% reactive liquids, such as polyurethanes or polyesters.

Wet lamination via waterborne or solvent based adhesives is confined to applications where at
least one substrate is porous (e.g., paper, cardboard, textiles) to facilitate drying. Once cured,
bond strength is generally high enough to cause failure or tearing of the porous substrate.
Most often, waterborne synthetic latex adhesives are utilized for wet bonding because of their
high initial strength and fast drying characteristics when applied to porous substrates.

Dry Lamination
Dry laminations are those in which the liquid adhesive is first dried before lamination. The
adhesive can be either applied to one substrate and dried or it can be applied as a hot melt type
of film (essentially another film layer). The adhesive is then in the dry solid or slightly tacky
stage when joined with the other substrate. The bonding is generally achieved during a high
temperature, high pressure nip. The temperature and pressure are sufficient to cause the
adhesive to flow and create an instantaneous bond when it cools and gels. Dry lamination can
be applied to a broader range of products such as film-to-film and film-to-foil.

Dry laminating adhesives are generally solvent based although considerable development has
taken place to reduce or replace the solvent to meet environmental regulations. This has
produced several strong competitors to conventional solvent-based adhesives such as:

hot melts (e.g., ethylene vinyl acetate copolymers),

100% reactive solids (e.g., two-part polyurethanes, one part moisture curing
polyurethanes and UV/EB curable acrylates),
high solids solvent based (e.g., silicone), and
waterborne adhesives (e.g., acrylic emulsions).

A significant advantage of reactive 100% solids adhesive in addition to the reduction in

possible VOCs is the possible elimination of drying ovens and resulting energy cost.
Hot melt adhesives are applied by heating the hot melt formulation to a closely controlled
temperature and applying via extrusion or die coaters. With hot melt adhesives, a pre-made
film of hot melt material may also be interleaved between two substrates at a high temperature
nip to achieve lamination.

Another method of making a laminate, which is outside the scope of this article, is
coextrusion. Coextrusion allows the production of a laminate in a single process. In this
process two or more thermoplastic materials are extruded separately and combined either
internally in the die or immediately after leaving the die. A separate adhesive is often not
required; however, certain film laminates may require the application of a "tie-coat" to
maximize adhesion of one film to the other. The coextrusion process is generally used for
very high volume laminate production.

Adhesive lamination is the preferred joining process when a specific film composition cannot
be effectively run in a coextrusion system due to equipment limitations or when the high
temperatures required in coextrusion would be harmful to the film. Adhesive lamination is
also preferred when the adhesive itself can provide additional functionality to the final
product.

3. Substrate Characteristics

The physical and chemical characteristics of the substrate itself will influence the choice of
adhesive and coating method to be employed. The substrates that are used in the manufacture
of flexible packaging fall into three main categories: papers, foils, and films. By far films are
becoming the dominant material because of their lightweight, strength, disposal, and cost
characteristics. Common polymeric films that are used in flexible packaging are listed in
Table 3.

High and low density polyethylene

Linear low density polyethylene
Cast and oriented polypropylene
Ethylene-vinyl acetate
Polyvinyl chloride
Cellulose (plain and coated)
Cast and oriented polyamide (nylon)
Polyester
Metallized film
Coated (polyvinylidene chloride or acrylic) film
Table 3: Common Polymeric Films Used in Flexible Packaging

The substrate could be sensitive to the water or solvent carrier employed or it could also be
affected by the heat of the drying oven. For example, the exposure to heat in an oven might
cause a substrate such as paper to dry excessively or to shrink and distort.
The stress applied by the laminator is another parameter that is important. During the
lamination process the substrate can experience unwinding, coating with adhesive, drying,
lamination in a nip, and rewinding. It also will pass over many idler rolls and undergo the
tension necessary to pull the films through the process. Certain films may be prone to web
breaks or tearing.

Proper surface preparations and selection of the right adhesive will help ensure a long lasting
bond and prevent delamination from occurring. In order for the adhesive to effectively wet
and bond to the substrate, the adhesive should have a surface tension that is ideally lower than
the critical surface tension of the substrate being coated. This may require the prebond surface
preparation of certain low surface energy films such as polyethylene, polypropylene, and the
fluorocarbons. Until recently such surface preparation of film was limited to flame or corona
treatment. However, new surface treating processes have been developed over the past several
years, which are aimed specifically at improving the efficiency of the lamination process.3

High-density atmospheric plasma represents a new generation of surface treatment technology

that is ideally suited for continuous polymer film lamination. Like corona treatment,
atmospheric plasma involves the electrical ionization of a gas. The plasma discharge creates a
smooth cloud of ionized gas that can react with the polymeric surface to raise its surface
energy and improve adhesion. However, unlike corona, plasma is created at much lower
voltage levels and temperatures.

An atmospheric plasma treatment system called Plasma 3 (Enercon Industries) has recently
been developed. This process can be applied at atmospheric pressures, unlike earlier low-
pressure plasma treatment. The major benefits of atmospheric plasma treatment are:

elimination of the need for a low pressure vessel and batch processing (as necessary
with conventional plasma treatment)
longer shelf-life treatments than possible with corona treatment
higher energy levels without degradation of the film
treatment of thicker substrates than can be used with corona.

Primer IT (Ciba) is another novel and versatile technology for improving the adhesion of UV
curable adhesives and coatings to polymeric substrates. The excellent adhesion is achieved by
the formation of covalent bonds between the surface and the coating. This active layer is
achieved by the application of a UV curable primer to the substrate after surface treatment but
before the application of the laminating adhesive. Prime IT technology allows the lamination
of virtually any kind of plastic material including low surface energy films such as BOPP.

4. The Laminating Adhesive

Selection of a particular adhesive system depends on a number of factors, all of which can
lead to problems unless they are properly understood or controlled. Common chemical,
physical, and performance factors are shown in Table 4.

• Mixing ratio of components

• Shelf-life of resins
Chemical
• Pot-life after mixing
• Curing time and energy required
• Molecular weight
• Solids content
Physical • Solution viscosity, melt viscosity
• Wetting behavior and coating ability
• Drying speed
• Initial bond strength (green tack)
• Ultimate bond strength
• Resistance to service environments
Performance
• Adaptability to laminating processes
• Laminating conditions (nip pressure, temperature, speed,
etc.)
Table 4: Factors Affecting the Selection of Flexible Packaging Adhesives

It should be noted that the adhesive in a laminate is often chosen for more than only its
bonding ability. In addition to holding the substrates together for the life of the laminate, the
adhesive might have to perform certain other functions that are necessary to the success of the
final product. These additional functions could include: increased or decreased gas
permeability, flame resistance, thermoforming capability, optical clarity, electrical insulation
or conductivity, chemical and heat resistance, etc.

The laminating adhesive must also be resistant to an effect called "tunneling". As illustrated in
Figure 2, tunneling is the localized separating or delamination of the substrates caused by two
films of different extensibility that stretch or relax at different rates. The localized stresses that
are produced can have a detrimental effect on the laminate's appearance and performance.

Figure 2: Tunneling in flexible laminates.1

 Figure 2: Relative peel strength of an acrylic latex
adhesive that is unmodified and modified with tackifier.

Other general considerations in selecting an adhesive for lamination include adhesion,

mechanical bond strength, formulating flexibility, and heat and chemical resistance. One must
also determine the ability of the adhesive to flow uniformly over the film's surface and form a
smooth continuous coating. The adhesive must be formulated so that any solvent or water
carrier can be removed either before the nip (through drying) or after (through porous
substrates).

Waterborne Laminating Adhesives

Waterborne laminating adhesives are commonly formulated from natural occurring materials,
such as dextrins, sodium silicates, and natural rubber, as well as synthetic organic polymer
emulsions based on vinyl acetate, acrylic, polyurethane, etc. The naturally occurring
adhesives are more commonly employed for labeling and other packaging applications;
whereas the synthetic emulsions are mostly used for either wet or dry laminating. Waterborne
laminating adhesives have become popular mainly due to governmental pressure for
laminating converters to reduce VOCs.

Although waterborne adhesives generally have poorer moisture and thermal resistance than
their solvent-based counterparts, the introduction of crosslinkers into the formulation has (1)
enabled waterborne adhesive to meet many of the performance criteria required and (2)
narrowed the performance gap between solvent-based and waterborne adhesives. There are
many types of waterborne laminating adhesives with widely differing applications and
performance properties. Only the more common waterborne laminating adhesives will be
reviewed in this article.

Acrylic emulsions offer a low cost adhesive with moderate performance properties. They are
tremendously versatile due to the large number of different monomers and resins available.
Acrylic waterborne laminating adhesives can provide bonds ranging from flexible and tough
to hard and rigid depending on the formulation. Acrylic adhesives inherently have very good
UV and oxidative stability and are generally preferred for outdoor applications.
Although acrylic emulsions can be used as laminating adhesives directly, they are often
formulated for specific applications. Tackifiers, for example, are added to provide improved
peel strength especially to low energy surfaces as shown in Figure 3.

Figure 3: UV cured adhesives can be applied as a

solventless, low viscosity liquid and then converted to a
solid or semi-solid state by radiation crosslinking.

For dry bonding, it should be noted that acrylics might require a longer dwell time than
crystalline polymers since they do not have a sharp melting or freezing point (as is typical of
most amorphous polymers). However, acrylic laminating adhesive are often used for dry
bonding in applications such as heat-seal food packaging and over-lays. For wet bonding
applications, the acrylics can also be formulated with varying degrees of tack and flexibility.
Generally the lower Tg polymers are used to manufacture flexible laminates. Examples of wet
laminating include bonding printed vinyl film to fabric for wallpaper and vinyl to foam for
furniture covering.

Table 5 provides a typical starting formation for a wet acrylic laminating adhesive.
Crosslinkers are often used to improve the heat and chemical resistance of waterborne acrylic
adhesives. These crosslinkers are generally either a polyfunctional aziridine or dispersible
isocyanate.

Parts by
Component
Weight
Rhoplex K-87 emulsion (Rohm and Haas) 100.0
Triton X-155 surfactant (10% solution in water)
2.5
(Rohm and Haas)
Water 2.0-5.0
Acrysol ASE-60 thickener (Rohm and Haas) 2.0-5.0
Diammonium phosphate (20% solution in water) 4.0
Total 110.5-116.5
Table 5: Formulation of a General Purpose Acrylic Laminating Adhesive

Typically, waterborne polyurethane adhesives also have high performance properties.

Waterborne polyurethane adhesives have been developed for standard laminating equipment
and fast line speeds. They generally provide excellent adhesion to a wide range of flexible
substrates and, when crosslinked, have strength greater than the substrates to which they are
attached. The primary disadvantage of polyurethane adhesives is their relatively high cost.

Polyurethane dispersions formed mainly of anionic polyesters and aliphatic isocyanates are
preferable for adhesives because of their higher degree of adhesion and resistance to UV light.
By varying the product's molecular weight, one can produce a wide range of end-properties.
Low molecular weight polyurethane dispersions yield adhesive with high hot tack and very
fast crystallization. The crystallization rate is an important parameter for thermoplastic
polyurethanes. It directly relates to the green strength and strength development rate.

Since waterborne polyurethanes are primarily linear polymers, their performance can be
greatly improved by the addition of crosslinking agents. A variety of crosslinkers are
available, including polyaziridenes, polyisocyanates, carbodiimides, epoxies, and epoxy
silanes. These systems differ significantly in reactivity, pot life, and the effect on final
properties.

Although waterborne acrylic and polyurethane adhesives are often dried at temperatures up to
95°C, the majority of the crosslinking reaction takes place in the finished laminate at ambient
temperatures. There is generally sufficient integrity after the laminating process so that slitting
or die cutting can be accomplished immediately after lamination even though the crosslinkers
have not fully reacted.

Another common laminating adhesive is a vinyl acetate / ethylene (VAE) copolymer that is
stabilized with polyvinyl alcohol. VAEs offer significant improvement over polyvinyl acetate.
Incorporation of ethylene into the vinyl acetate backbone decreases glass transition
temperature and provides superior flexibility and adhesion.

A more recent development has been vinyl acetate acrylic (VAA) copolymers. VAA
adhesives have excellent strength, setting speed, compatibility with common formulating raw
materials, and emulsion stability (some are even freeze / thaw stable). VAA copolymers can
be made to be soft and pressure sensitive or hard and tack free. VAAs generally offer lower
glass transition temperature than VAEs. The incorporation of carboxyl functionality provides
reactive groups for crosslinking.

Solvent-Based Laminating Adhesives

Solvent-borne laminating adhesives can be formulated from many of the same polymers
described above for waterborne systems. Acrylic solvent solutions, for example, have
especially found application when a high degree of environmental resistance and non-
yellowing properties are required. They can be used for wet laminating, but are generally
found in dry laminating applications. The speed of which the solvent evaporates is a
significant benefit in most production operations. Because of the lack of emulsifiers and
surfactants, the moisture resistance of solvent-based adhesive is generally superior to
waterborne systems.

One of the most popular solvent based laminating adhesives is polyester. Introduced in the
1950s for laminating polyester film, solvent borne polyester resins contain relatively low
solids (20-30%). These materials provide excellent adhesion to polyester film and very good
adhesion to many other polymeric films and metal foils.
The reaction of the hydroxyl of the polyester with a polyisocyanate produces a crosslinked
adhesive network with very good thermal and chemical resistance. The polyester laminating
adhesives have high green strength, are fairly fast curing, and well suited to fast production
processes.

Due to environmental regulations, polyester adhesive systems with reduced VOCs and solvent
recovery and incineration systems have been developed. Polyester solution adhesive of 40-
50% solids content were developed to provide excellent adhesion properties, but they have
lower green strength than the low solids products.

Solventless Laminating Adhesives

Major changes have occurred in 100% reactive solventless adhesives over the last decade.
The first solventless laminating adhesives were primarily moisture-cured polyurethanes. The
adhesive is coated onto a substrate and atmospheric moisture reacts with excess isocyanate
groups to crosslink the adhesive after the secondary film has been joined. Slitting of the
laminate generally can occur in 24-72 hours.

While water based systems have been developed as an economic alternative to overcome
some of the drawbacks associated with solvent, in practice the performance of water based
adhesives, especially in wet environments, is not as good as their solvent counterparts. The
most important solventless and high solids adhesives used in laminating flexible packaging
are those belonging to the polyurethane family (Table 6).

Type Solvent Curing Mechanism

Ester or Reaction with moisture in
One component
ketone atmosphere or on substrate surface
Two component; high Ester or Reaction between isocyanate
solids ketone terminated resin and polyol
Two component; low or Ester or Reaction between an isocyanate and
medium solids ketone polyol
• Reaction with moisture in
atmosphere or on substrate surface
100% solids None
• Reaction between isocyanate
terminated resin and polyol
Table 6: Polyurethane Laminating Adhesive

Two-part solventless polyurethanes were also developed to negate some of the disadvantages
of the moisture cured type, such as bubbling, inconsistent cure rate, and cloudiness. These
problems were generally associated with variations in the ambient moisture content. The two-
part polyurethane laminating adhesives require a mixing and metering unit since pot life is
limited. High residual monomers and low initial bond strengths somewhat limit the
application of these adhesives.

An improved polyurethane adhesive has been developed based on moderately high viscosity
polyurethane polymers that require a 50-70°C application temperature. The increased
viscosity reduces the cure time to 12-24 hours before slitting. This generation of adhesive is
made from a process that removes nearly all of the excess isocyanate monomer from the
prepolymer.4

Hot Melt Laminating Adhesives

Hot melt adhesives used in the laminating process are 100% solid polyester, polyamides,
EVAs, polyethylene, and thermoplastic and reactive urethane adhesives which are applied at
ambient temperature to a substrate and activated using heat. A second substrate is introduced
for laminating to the first after the material is activated.

Accurate applications require that dry hot melt adhesive first undergo a converting operation,
which modifies their raw, physical form (pellets or granules) to webs or films. Web and film
adhesives are created by melting the granules or pellets and extruding them into rolls of
adhesives.

Hot melt adhesive can also be applied directly to the substrate. The adhesive (pellets, pillows,
granules, or bulk filled drums) is melted and applied to the substrate via rotogravure, spray, or
extrusion coating technology. Significant material savings and line speeds can result by direct
application of hot melt adhesives.

UV Curable Laminating Adhesives

Ultraviolet light (UV) or electron beam (EB) curing laminating adhesives are creating
significant interest for flexible packaging. Acrylate / methacrylate monomers and oligomers
as well as photoinitiators are essential components of UV adhesives. Similar monomers and
oligomers are used in EB adhesives, but they do not require photoinitiators. Aliphatic
urethane acrylates are commonly used in laminations since they have good adhesion to most
films and are non-yellowing. These adhesives are also characterized by a very low application
viscosity, on the order of 350-450 cps. Table 7 shows a typical formulation for such an
adhesive.

Parts by
Component
Weight
CN135, Laminating Adhesive Oligomer (Sartomer
91.0
Company)
CN966H90 Urethane Acrylate Oligomer (Sartomer
6.0
Company)
Adhesion Promoter (Ciba) 2.5
Irgacure 819, Photoinitiator (Ciba) 0.5
Total 100.0
Table 7: Standard UV Curable Laminating Adhesive Formulation 5

UV/EB laminating adhesives are directly coated on the surface of the film, nipped and cured
as shown in Figure 4. Line speed can be adjusted by using UV lamps of different intensity.
These adhesives were developed primarily as low VOC laminating systems but offer a
number of potential advantages over solvent-based, waterborne, and solventless adhesive
systems. These advantages include:

bond strength is achieved immediately on cure

the adhesive is a one-component system with long shelf life
the adhesive remains unchanged until cured and no viscosity adjustments are required
UV/EB systems can be cured at room temperature
significant number of raw materials with broad formulation range to meet many
widely differing performance requirements.

Upon curing, these adhesives offer a non-tacky film that provides excellent adhesive strength
to a number of different substrates. However, when a specific application requires laminating
opaque substrates, EB-curing adhesives may be necessary, since EB cure is not negatively
affected by an opaque substrate.

References

1. Brewis, D.M., and Briggs, D., Industrial Adhesive Problems, John Wiley & Sons,
New York, 1985, pp. 247-250.
2. Mausar, J., "Manufacturing Pressure Sensitive Adhesive Products: A Coating and
Laminating Process", Adhesives and Sealants Industry, April, 2005.
3. Petrie, E.M., "Trends in Adhesive Primers / Surface Treatments",
SpecialChem4Adhesives, October 20, 2004.
4. Voss, P.A., "WB, 100% Solids Adhesives for Flexible Packaging Provide Solvent
Alternative", Adhesives Age, May 1998.
5. Smith, D.A., "A Cure for Laminating Adhesives", Adhesives Age, August 2001.