Laminating Adhesives for Flexible Packaging
by Edward M. Petrie
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Introduction Wet and Dry Lamination Substrate Characteristics 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 endproducts 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.
Thicker laminates (e. wood laminates) can be produced by bonding substrates in a hot press.
. The specific formulations will heavily depend on the nature of the laminating process employed. These are generally classified as either wet or dry laminating processes and they are described in Table 1. Specific processes differ primarily by how the adhesive is applied and converted from a liquid to a solid.Each category has a number of applicable base polymers and a wide variety of formulation possibilities. This article will provide a primer on laminating adhesives and processes used mainly for flexible packaging. Wet and Dry Lamination
The manufacture of film laminates is a relatively simple continuous process of coating and bonding. decorative laminates. Generic illustrations of typical flexible laminate production lines are shown in Figure 1. However. and the final physical properties desired.g. these adhesives are outside the scope of this article.
2.. There are several laminating processes that can be easily adapted to production. the nature of the film substrate. followed by a general discussion of the main adhesive systems that are usually employed. The principles of the wet and dry laminating processes will be discussed first.
and then bonded only with Cold seal slight pressure (formulated so that tack to non-cold seal surfaces is minimized) Wet Processes Liquid adhesive is Wet bond applied to a substrate. extruder Polyurethane dispersions. laminating then immediately Hot melt seal coating Heated rotogravure cylinder. acrylic / natural rubber
Gravure cylinder or smooth roll
Polyurethane dispersions. water-based polyvinyl alcohol. emulsions. water-
. modified polyolefins. acrylic. and then application laminating laminated to a second cylinder substrate via a heated compression nip. dried with heat and air Gravure Dry bond flow. acrylic. Low viscosity hot melt adhesives are applied to substrate and then later A liquid adhesive is applied. dried with heat and air. emulsions. polyesters
Same are dry bonding
Synthetic rubber. ethylene vinyl acetate copolymers. Typical Application Equipment
Dry Processes A liquid adhesive is coated on a substrate. silicone solvent Ethylene vinyl acetate.Figure 1: Relative peel strength of an acrylic latex adhesive that is unmodified and modified with tackifier. acrylic solvent.
000Emulsion. full bond strength generally occurs over about a period of 24 hours. There are a number of coating methods that can be used depending on the nature of the adhesive. 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 Polyurethanes. adhesive coater. Therefore. 100% 500.000 emulsion roll Solution. and laminator.laminated to a second based polyvinyl substrate via a nip alcohol. Knife over 4.000 15-100 emulsion Solution. 100% Slot die 200. Weight. 10 100-200 Wire rod 100-1.% Coating Speed. Specific applications may require varying degrees of adhesive coating thickness. m/min With either wet or dry laminating. It is then mated 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. Table 2 shows a summary of some of the capabilities and limitations of common coating methods that are used in producing laminates. 50. initial tack or "green strength" is often an important criterion for a
. 2 100-700 Gravure 15-1500 2-50 emulsion Emulsion. hot 20-500 2 100-500 melt Curtain 125.00025-750 10 100-150 emulsion.000 Table 2: Summary of Capabilities / Limitations of Common Coating Methods 2 Coating Viscosity.000 die solids Emulsion. +/. Type of Coating Adhesives Method Commonly Used Solution. Solventless substrata in liquid application roll polyesters laminating form.000 solids 50. Reverse 30025-250 5 100-400 50.000 roll 100% solids Solution. hot 40020-700 2 100-300 melt. cps gm/m2 Coating Accuracy. hot Extrusion 40015-750 5 300-700 melt.
Once cured.g. The coated substrate is then nipped with another substrate. such as polyurethanes or polyesters. acrylic emulsions). This has produced several strong competitors to conventional solvent-based adhesives such as: hot melts (e. 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 temperature and pressure are sufficient to cause the adhesive to flow and create an instantaneous bond when it cools and gels. The bonding is generally achieved during a high temperature. 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.g. The types of adhesive used for wet lamination are: waterborne natural products. 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 adhesive is then in the dry solid or slightly tacky stage when joined with the other substrate. These include the application of UV or electron beam for crosslinking and the addition of chemical crosslinking agents in the adhesive formulation.laminating adhesive.
With wet laminations. and waterborne adhesives (e. Dry laminating adhesives are generally solvent based although considerable development has taken place to reduce or replace the solvent to meet environmental regulations.. ethylene vinyl acetate copolymers).
. high pressure nip..
Dry laminations are those in which the liquid adhesive is first dried before lamination. usually by roller coating or air knife.g. silicone).. waterborne synthetic latex adhesives are utilized for wet bonding because of their high initial strength and fast drying characteristics when applied to porous substrates. the adhesive is applied to one substrate. etc. 100% reactive liquids.g. 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. one part moisture curing polyurethanes and UV/EB curable acrylates). Various technologies have been developed to either speed the strength development or to provide improved properties in laminated products. acrylic. Most often. Wet lamination via waterborne or solvent based adhesives is confined to applications where at least one substrate is porous (e. such as starch and dextrin or waterborne synthetic latex products. paper. cardboard. Dry lamination can be applied to a broader range of products such as film-to-film and film-to-foil. two-part polyurethanes. bond strength is generally high enough to cause failure or tearing of the porous substrate. textiles) to facilitate drying.g. high solids solvent based (e.. 100% reactive solids (e. such as polyvinyl acetate..
certain film laminates may require the application of a "tie-coat" to maximize adhesion of one film to the other. disposal. Coextrusion allows the production of a laminate in a single process. For example. Substrate Characteristics The physical and chemical characteristics of the substrate itself will influence the choice of adhesive and coating method to be employed.
. 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. a pre-made film of hot melt material may also be interleaved between two substrates at a high temperature nip to achieve lamination. is coextrusion. the exposure to heat in an oven might cause a substrate such as paper to dry excessively or to shrink and distort. 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. By far films are becoming the dominant material because of their lightweight. and films. however. which is outside the scope of this article. Another method of making a laminate. The coextrusion process is generally used for very high volume laminate production. foils. strength. In this process two or more thermoplastic materials are extruded separately and combined either internally in the die or immediately after leaving the die. With hot melt adhesives.
3. Adhesive lamination is also preferred when the adhesive itself can provide additional functionality to the final product.Hot melt adhesives are applied by heating the hot melt formulation to a closely controlled temperature and applying via extrusion or die coaters. A separate adhesive is often not required. Common polymeric films that are used in flexible packaging are listed in Table 3. The substrates that are used in the manufacture of flexible packaging fall into three main categories: papers. and cost characteristics.
However. Primer IT (Ciba) is another novel and versatile technology for improving the adhesion of UV curable adhesives and coatings to polymeric substrates. 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. During the lamination process the substrate can experience unwinding. This may require the prebond surface preparation of certain low surface energy films such as polyethylene. drying. Proper surface preparations and selection of the right adhesive will help ensure a long lasting bond and prevent delamination from occurring. This process can be applied at atmospheric pressures. which are aimed specifically at improving the efficiency of the lamination process. The excellent adhesion is achieved by the formation of covalent bonds between the surface and the coating. Until recently such surface preparation of film was limited to flame or corona treatment. and rewinding. atmospheric plasma involves the electrical ionization of a gas. Prime IT technology allows the lamination of virtually any kind of plastic material including low surface energy films such as BOPP. plasma is created at much lower voltage levels and temperatures. the adhesive should have a surface tension that is ideally lower than the critical surface tension of the substrate being coated. It also will pass over many idler rolls and undergo the tension necessary to pull the films through the process. The Laminating Adhesive
. unlike corona. An atmospheric plasma treatment system called Plasma 3 (Enercon Industries) has recently been developed. Certain films may be prone to web breaks or tearing. However. polypropylene.3 High-density atmospheric plasma represents a new generation of surface treatment technology that is ideally suited for continuous polymer film lamination. and the fluorocarbons.The stress applied by the laminator is another parameter that is important.
4. new surface treating processes have been developed over the past several years. lamination in a nip. 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. coating with adhesive. 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. Like corona treatment. In order for the adhesive to effectively wet and bond to the substrate. unlike earlier lowpressure plasma treatment.
speed. The localized stresses that are produced can have a detrimental effect on the laminate's appearance and performance.1
. physical. These additional functions could include: increased or decreased gas permeability. etc. optical clarity. In addition to holding the substrates together for the life of the laminate.
Figure 2: Tunneling in flexible laminates.) 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. electrical insulation or conductivity. • 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. all of which can lead to problems unless they are properly understood or controlled. tunneling is the localized separating or delamination of the substrates caused by two films of different extensibility that stretch or relax at different rates. temperature. 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. flame resistance. etc. The laminating adhesive must also be resistant to an effect called "tunneling". thermoforming capability. chemical and heat resistance. As illustrated in Figure 2. the adhesive might have to perform certain other functions that are necessary to the success of the final product. and performance factors are shown in Table 4.Selection of a particular adhesive system depends on a number of factors. Common chemical.
Other general considerations in selecting an adhesive for lamination include adhesion. acrylic. The naturally occurring adhesives are more commonly employed for labeling and other packaging applications. Acrylic adhesives inherently have very good UV and oxidative stability and are generally preferred for outdoor applications. Waterborne laminating adhesives have become popular mainly due to governmental pressure for laminating converters to reduce VOCs. 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). sodium silicates. One must also determine the ability of the adhesive to flow uniformly over the film's surface and form a smooth continuous coating.Figure 2: Relative peel strength of an acrylic latex adhesive that is unmodified and modified with tackifier. and heat and chemical resistance.
. Although waterborne adhesives generally have poorer moisture and thermal resistance than their solvent-based counterparts. formulating flexibility. etc. Only the more common waterborne laminating adhesives will be reviewed in this article.
Waterborne Laminating Adhesives
Waterborne laminating adhesives are commonly formulated from natural occurring materials. 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. They are tremendously versatile due to the large number of different monomers and resins available. whereas the synthetic emulsions are mostly used for either wet or dry laminating. Acrylic waterborne laminating adhesives can provide bonds ranging from flexible and tough to hard and rigid depending on the formulation. such as dextrins. and natural rubber. Acrylic emulsions offer a low cost adhesive with moderate performance properties. as well as synthetic organic polymer emulsions based on vinyl acetate. polyurethane. mechanical bond strength.
acrylic laminating adhesive are often used for dry bonding in applications such as heat-seal food packaging and over-lays. 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. Generally the lower Tg polymers are used to manufacture flexible laminates.0 Diammonium phosphate (20% solution in water) 110. they are often formulated for specific applications. Tackifiers. are added to provide improved peel strength especially to low energy surfaces as shown in Figure 3. For dry bonding.Although acrylic emulsions can be used as laminating adhesives directly. Component Parts by Weight 100. For wet bonding applications. waterborne polyurethane adhesives also have high performance properties.5-116.0-5.0 Water 2. low viscosity liquid and then converted to a solid or semi-solid state by radiation crosslinking. Examples of wet laminating include bonding printed vinyl film to fabric for wallpaper and vinyl to foam for furniture covering.
Figure 3: UV cured adhesives can be applied as a solventless.0-5.0
Rhoplex K-87 emulsion (Rohm and Haas) Triton X-155 surfactant (10% solution in water) 2. They generally provide excellent adhesion to a wide range of flexible
. Waterborne polyurethane adhesives have been developed for standard laminating equipment and fast line speeds.0 Acrysol ASE-60 thickener (Rohm and Haas) 4.5 Total Table 5: Formulation of a General Purpose Acrylic Laminating Adhesive Typically. However. the acrylics can also be formulated with varying degrees of tack and flexibility. for example. Table 5 provides a typical starting formation for a wet acrylic laminating adhesive.5 (Rohm and Haas) 2. 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).
Acrylic solvent solutions. It directly relates to the green strength and strength development rate. VAEs offer significant improvement over polyvinyl acetate. have especially found application when a high degree of environmental resistance and nonyellowing properties are required. The speed of which the solvent evaporates is a significant benefit in most production operations. Because of the lack of emulsifiers and surfactants. By varying the product's molecular weight. for example.
Solvent-Based Laminating Adhesives
Solvent-borne laminating adhesives can be formulated from many of the same polymers described above for waterborne systems. their performance can be greatly improved by the addition of crosslinking agents. but are generally found in dry laminating applications. 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. have strength greater than the substrates to which they are attached. solvent borne polyester resins contain relatively low solids (20-30%).substrates and. Since waterborne polyurethanes are primarily linear polymers. A variety of crosslinkers are available.
. the moisture resistance of solvent-based adhesive is generally superior to waterborne systems. These materials provide excellent adhesion to polyester film and very good adhesion to many other polymeric films and metal foils. A more recent development has been vinyl acetate acrylic (VAA) copolymers. VAA adhesives have excellent strength. 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. including polyaziridenes. VAAs generally offer lower glass transition temperature than VAEs. epoxies. Although waterborne acrylic and polyurethane adhesives are often dried at temperatures up to 95°C. and emulsion stability (some are even freeze / thaw stable). one can produce a wide range of end-properties. They can be used for wet laminating. The crystallization rate is an important parameter for thermoplastic polyurethanes. The incorporation of carboxyl functionality provides reactive groups for crosslinking. compatibility with common formulating raw materials. carbodiimides. The primary disadvantage of polyurethane adhesives is their relatively high cost. Another common laminating adhesive is a vinyl acetate / ethylene (VAE) copolymer that is stabilized with polyvinyl alcohol. the majority of the crosslinking reaction takes place in the finished laminate at ambient temperatures. polyisocyanates. Low molecular weight polyurethane dispersions yield adhesive with high hot tack and very fast crystallization. One of the most popular solvent based laminating adhesives is polyester. and epoxy silanes. Incorporation of ethylene into the vinyl acetate backbone decreases glass transition temperature and provides superior flexibility and adhesion. VAA copolymers can be made to be soft and pressure sensitive or hard and tack free. These systems differ significantly in reactivity. Introduced in the 1950s for laminating polyester film. and the effect on final properties. setting speed. pot life. when crosslinked.
High residual monomers and low initial bond strengths somewhat limit the application of these adhesives. These problems were generally associated with variations in the ambient moisture content. in practice the performance of water based adhesives. are fairly fast curing. polyester adhesive systems with reduced VOCs and solvent recovery and incineration systems have been developed. 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. The twopart polyurethane laminating adhesives require a mixing and metering unit since pot life is limited. An improved polyurethane adhesive has been developed based on moderately high viscosity polyurethane polymers that require a 50-70°C application temperature. The most important solventless and high solids adhesives used in laminating flexible packaging are those belonging to the polyurethane family (Table 6). The first solventless laminating adhesives were primarily moisture-cured polyurethanes. The polyester laminating adhesives have high green strength. but they have lower green strength than the low solids products.The reaction of the hydroxyl of the polyester with a polyisocyanate produces a crosslinked adhesive network with very good thermal and chemical resistance. and cloudiness. is not as good as their solvent counterparts. and well suited to fast production processes. such as bubbling. low or Ester or ketone medium solids Curing Mechanism Reaction with moisture in atmosphere or on substrate surface Reaction between isocyanate terminated resin and polyol Reaction between an isocyanate and polyol • Reaction with moisture in atmosphere or on substrate surface None 100% solids • 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. Polyester solution adhesive of 4050% solids content were developed to provide excellent adhesion properties. Type Solvent Ester or One component ketone Two component. Slitting of the laminate generally can occur in 24-72 hours. especially in wet environments. inconsistent cure rate.
Solventless Laminating Adhesives
Major changes have occurred in 100% reactive solventless adhesives over the last decade. Due to environmental regulations. high Ester or ketone solids Two component. While water based systems have been developed as an economic alternative to overcome some of the drawbacks associated with solvent. The increased viscosity reduces the cure time to 12-24 hours before slitting. This generation of adhesive is
Photoinitiator (Ciba) 100.made from a process that removes nearly all of the excess isocyanate monomer from the prepolymer. spray. EVAs. Similar monomers and oligomers are used in EB adhesives. nipped and cured as shown in Figure 4. or extrusion coating technology. Accurate applications require that dry hot melt adhesive first undergo a converting operation. polyethylene. which modifies their raw. granules. Table 7 shows a typical formulation for such an adhesive.
UV Curable Laminating Adhesives
Ultraviolet light (UV) or electron beam (EB) curing laminating adhesives are creating significant interest for flexible packaging. Web and film adhesives are created by melting the granules or pellets and extruding them into rolls of adhesives.0 Company) CN966H90 Urethane Acrylate Oligomer (Sartomer 6. but they do not require photoinitiators. or bulk filled drums) is melted and applied to the substrate via rotogravure. Significant material savings and line speeds can result by direct application of hot melt adhesives. 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. These adhesives were developed primarily as low VOC laminating systems but offer a
.5 Adhesion Promoter (Ciba) 0. Acrylate / methacrylate monomers and oligomers as well as photoinitiators are essential components of UV adhesives. polyamides. physical form (pellets or granules) to webs or films. and thermoplastic and reactive urethane adhesives which are applied at ambient temperature to a substrate and activated using heat.5 Irgacure 819. pillows. The adhesive (pellets. on the order of 350-450 cps.0 Total Table 7: Standard UV Curable Laminating Adhesive Formulation 5 UV/EB laminating adhesives are directly coated on the surface of the film.4
Hot Melt Laminating Adhesives
Hot melt adhesives used in the laminating process are 100% solid polyester.0 Company) 2. Laminating Adhesive Oligomer (Sartomer 91. A second substrate is introduced for laminating to the first after the material is activated. Component Parts by Weight
CN135. Hot melt adhesive can also be applied directly to the substrate. Line speed can be adjusted by using UV lamps of different intensity.
E. 2005. 247-250. D. D. 4. April. May 1998. waterborne. Voss.. these adhesives offer a non-tacky film that provides excellent adhesive strength to a number of different substrates.. pp. 5. Upon curing. August 2001. Mausar. References 1. "Trends in Adhesive Primers / Surface Treatments". However. 2004..M. John Wiley & Sons. J. and solventless adhesive systems. Adhesives Age.M. Industrial Adhesive Problems.A. Petrie. and Briggs. New York.
. Brewis. "A Cure for Laminating Adhesives". 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. Smith. EB-curing adhesives may be necessary. 1985. SpecialChem4Adhesives. P.. "Manufacturing Pressure Sensitive Adhesive Products: A Coating and Laminating Process". October 20. 2.. Adhesives Age. since EB cure is not negatively affected by an opaque substrate. "WB.. when a specific application requires laminating opaque substrates. D. Adhesives and Sealants Industry. 100% Solids Adhesives for Flexible Packaging Provide Solvent Alternative".A. 3.number of potential advantages over solvent-based.