environmental legislation to reduce volatile organic compound (VOC) emissions, the exi- ble lm and paper laminating industry is rapid- ly changing from solvent-based adhesives to new water-based polyurethane adhesives and acrylic emulsions for dry-bond laminating. In addition, very low residual monomer 100 per- cent solids systems are rapidly gaining accep- tance as an alternative technology to tradition- al dry-bond laminating techniques. Dry-bond laminating is the process of coating either a solvent-based or water-based adhesive to a substrate, drying the adhesive with heat and airow and then lami- nating the adhesive to a second substrate via a heated compressi on ni p that mates the fi l ms together. Solventless laminating, on the other hand, involves metering a low-viscosity adhesive onto a multiple-appli- cation roll conguration that applies the adhesive to the rst substrate, which is then mated to a second substrate using a heated nip. Whether the laminating technique is dry-bond or solventless, adhesive coating weights are typically 1.0 1. 5 lbs. per 3,000 ft., requiring a relatively small adhesive coating weight to meet the nished lami- nate performance requirements. A typical laminating converters product line is com- posed of structures using polyolenic lms such as poly- ethylene terephthalate, polypropylene and polyethylene I WATE R- B AS E D ADHESIVES SOLVENTLESS LAMINATION REDUCES FLEXIBLE PACKAGING VOCS I By Peter A. Voss Editors Note: The following article is based on a presentation given by Peter A. Voss, Global Program Manager-Flexible Packaging, H.B. Fuller Co., at a Flexo on Unsupported Film seminar in Spring 2001. The seminar was sponsored by Akzo Nobel Inks at the companys Center for Technical Excellence in Plymouth, MN. For more information on Akzo Nobel Inks sem- inars, contact Emily Horn at (800) 328-7838, ext. 326. HOT TECHNOLOGIES I Laminator Lamination Unwind Print and Lamination Rewind Stock Unwind Central Impression Press Adhesive Applicator This six-color central-impression press has been modified for laminating after printing. 2 as well as paper and aluminum foil. The nished lamina- tions can be used for a variety of end-use applications, although food packaging consumes the largest portion of these laminations. Whi l e t here are many appl i cat i ons for f l exi bl e packaging laminates, there are relatively few key perfor- mance requirements that they all share. The adhesives must have excellent clarity and bond strengths as well as be resistant to extremes of heat and humidity. In addition, the adhesive must be resistant to tunneling. Tunneling is the localized separating or delamination of the two substrates being bonded together. Tunneling often occurs when the two films differ in extensibility, and stretch or relax at different rates. These localized delaminations can have a detrimental effect on package appearance and a potentially damaging effect on the package contents, and remains the major concern for most converters. Water-Based Adhesives The flexible packaging adhesive market is estimated at $130 million, of which approximately only 25 percent is supplied by either acrylic emulsions or polyurethane dis- persions (PUDs). Aside from governmental pressure for laminating converters to switch from solvent-based prod- ucts to waterborne, there has been little incentive for these converters to make a change. The introduction of improved crosslinkers (catalysts to increase the perfor- mance of the adhesive) such as dispersible iso- cyanates, polyfunctional aziridines and polyfunctional carbodiimides enables the water-based adhesives to meet many of the performance criteria when the lamina- tion is subject to extremes of heat and humidity and is narrowing the performance gap between solvent-based and water-based adhesives. Polyurethane Dispersions. In comparison to conven- tional solvent-based polyurethanes, PUDs are the closest performing water-based polymers in terms of adhesion and resistance properties that are commercially avail- able. PUDs typically have very low solution particle sizes (<75nm). The particle size of a water-based adhesive directly relates to the machinability (how well the product runs on the equipment) of the adhesive on laminating equipment and the ability to operate at maximum line speeds. In addition, the low particle size enhances the dried adhesives clarity to a level comparable to solvent- based products. The main drawback to PUDs is cost. PUDs are based on aliphatic diisocyanates such as isophorone diisocyanate and tetramethylxylene diiso- cyanate, which are significantly more expensive than toluene diisocyanate, which is used in most solvent- based polyurethanes. Acrylic Emulsions. Acrylic emulsions offer the lami- nating converter a low-cost product with moderate perfor- mance properties, which often meets their requirements for less stringent applications. In some cases, acrylics do not meet converter requirements, in that the adhesion and resistance properties are less than those of PUDs and conventional solvent-based products. In addition, acrylic polymers historically used in dry-bond laminating had very poor machinability and required chilling the roll to prevent the adhesive from coagulating. These acrylics also suffered from a tendency to foam, which, in combination with the machining issues, severely limited the speed at which a converter could run the lami- nator. Thus, much of the price advantage gained by using a low-cost acrylic was erased by the decreased efficiency of the laminating equipment. New commercially available acrylic polymers are avail- able with excellent machining properties that can be used I HOT TECHNOLOGIES Laminator Lamination Unwind Rewind Print Unwind Central Impression Press Adhesive Applicator This in-line laminating setup incorporates a separate and self-contained laminating machine in-line with the flexo press. 3 at maximum dry-bond laminator line speeds of 700-800 fpm. In addition, when it is crosslinked with either a poly- functional aziridine or dispersible isocyanate, the adhe- sive system meets many of the heat and humidity resis- tance properties that only a PUD could achieve. Crosslinking Chemistry. Crosslinking a water-based adhesive imparts a lamina- tion with the necessary resistance properties to maintain the package integrity when hot-lled, boiled or stored in a refrigerated case. In addition, crosslinking the adhesive significantly increases bond strengths and reduces the possibility of tunneling. There are several commercially available crosslinkers for water-based polymers, each differing in reactivity, pot life (the length of time the adhesive can be used after a crosslinker is added) and effect on nal properties. It should be noted that the adhesive polymers used with these crosslinkers are anion- ic (stable in water), having carboxylic functionality in the back- bone (reacts with the crosslinker), which is neutralized with a volatile tertiary amine or ammonia. The presence of the car- boxylate salt renders the polymer dispersible or emulsiable in water. Pot life is always a consideration with any two-compo- nent ambient cure system. Reactions that occur through the carboxylic acid functionality tend to have an excellent pot life of eight to 10 hours because these reactions are typically alkali-hindered. Polymers neutralized with ammo- nia or an amine routinely have a pH >7.5. As the ammonia or tertiary amine volatilizes during the drying process, the carboxylic acid functionality becomes available to react with the crosslinker. The isocyanate-hydroxyl reaction is com- mon for solvent-based adhesive systems, resulting in exceptional properties. When dispersible isocyanate crosslinkers are used with water-based polymers, the sys- tems are plagued by the isocyanate-water side reaction. As a result of this reaction, dispersible isocyanate systems are limited to pot lives of four to six hours in order to maintain performance properties. Although the water-based adhesives are dried at ele- vated temperatures of up to 200 degrees F., due to short dwell times of two to four seconds in the drying ovens it is believed that the majority of the crosslinking reaction takes place in the nished lamination at ambient temper- atures, which are usually 77 degrees F. Heat-aging a dry- bond lamination is not always required. In most cases, a lamination can be cut or slit to its nal size almost imme- diately after laminating. Even though the crosslinkers have not fully reacted with the base polymer, there is still enough laminate integrity for the slitting operation. This in turn enables a laminator to produce material on a just-in- time basis. Aside from the actual equipment used in pro- duction, the rapid turnaround time of dry-bond laminating is the most critical difference between dry-bond laminating and solventless laminating. Solventless Adhesives First-Generation Adhesives. The first solventless laminating adhesives developed were polyurethane mois- ture-curing products. These adhesives are made from isocyanate prepolymers, the reaction product of a polyol with excess isocyanate. The prepolymers are high in vis- cosity, which gives excellent initial bond strengths; how- ever, they require an application temperature of 90 to 100 degrees C. The adhesive is coated onto the primary lm and atmospheric moisture reacts with the excess iso- cyanate groups to crosslink the adhesive after the sec- ondary lm has been mated to the primary lm; slitting can usually take place in 24 to 72 hours. First-generation curing mechanism: R-NCO + H2O _ R-NH2 + CO2 R-NH2 + R-NCO _ R-NHCOHN-R The problems encountered with using these rst-gen- eration adhesives are bubbles in the lamination, a cloudy appearance in clear lms and inconsistency of the cure rate. The bubbles are produced by the by-product carbon dioxide of the curing reaction, and can be trapped when high-barrier films are laminated. The amount of atmos- pheric moisture that comes in contact with the adhesive as it is coated can lead to a cloudy appearance in clear films and an inconsistency in the cure rate. Moisture is often added to the primary film by means of a spray boom just prior to nipping the secondary film. This will increase the rate of cure, but it also reduces the clarity of the laminated lm by leaving a cloudy appearance. This cloudy appearance can readily be seen in clear laminations and in clear package window areas of printed structures. Second-Generati on Adhesi ves. The next maj or advancement in solventless laminating adhesives was the development of two-part polyurethane adhesives. These products are comprised of a polyurethane prepoly- mer and a polyol, both low in viscosity. The components are mixed together with a meter-mix-dispensing unit at room temperature and pumped onto the coating station of the laminator through an in-line static mixer. The meter-mix in combination with the static mixer ensures that the proper ratio of adhesive components is present and completely mixed, resulting in a consistent cure rate. Second-generation curing mechanism: R-NCO + HO-R _ R-NHCOO-R The problems encountered with using these second- generation adhesives are low initial bond strengths and the presence of high residual monomer. The low initial bonds are a result of the low viscosity of both adhesive compo- nents, which means tighter laminator controls are needed to prevent laminations from tunneling before the adhesive has a chance to properly cure. Slitting the lamination can only take place after a 12- to 48-hour cure time. The high residual isocyanate monomer causes a phenomenon known as anti-seal. This occurs when the isocyanate 4 I HOT TECHNOLOGIES monomer migrates through a soft sealant lm such as poly- ethylene and reacts with atmospheric moisture. This reac- tion creates a very hard and thermally stable polyurea layer that renders the laminate unsealable. In addition to the anti- seal problems, there are possible health risks due to worker exposure from the high-residual monomer. Finally, the pres- ence of isocyanate monomer requires EPA documentation and reporting, which can be a time-consuming burden for any laminating converter. To address the problems associated with using rst- or second-generation solventless adhesives, third-genera- tion two-part polyurethane adhesive systems that have a consi stent cure rate, l ow resi dual monomer and increased initial bond strengths have been developed. Third-Generation Adhesives. Typical third-generation adhesives are based on moderate-viscosity polyurethane polymers that require a 50-degree C. to 70-degree C. application temperature. The increased viscosity of the third-generation versus second requires a 12- to 24-hour cure time before slitting. The third-generation adhesives are made from a process that removes nearly all of the excess isocyanate monomer from the prepolymer compo- nent, consistently resulting in a blended adhesive system with less than 0.08 percent free isocyanate. The low residual isocyanate monomer eliminates the anti-seal issue, health concerns from worker exposure to iso- cyanate monomers and the regulatory documentation associated with isocyanates. Third-generation curing mechanism: R-NCO + HO-R _ R-NHCOO-R The majority of solventless laminators in the United States are still applying a second-generation adhesive system. The meter mix dispensing units are not generally equipped with heating capabilities. In order for a laminat- ing converter to begin using a third-generation adhesive, a capital expenditure to update their meter-mix-dispens- ing unit with heating capabilities is necessary. This capital expenditure can often delay the conversion to a third-gen- eration adhesive or altogether discourage a converter from changing to a third-generation system. To overcome this hurdle and keep the equipment expenses associated with using a third-generation adhe- sive system minimal, a third-generation adhesive has been developed that can be pumped and mixed at room temperature through existing meter-mix dispensing units used with second-generation products. This system gives a laminating converter the many benets of using a third- generation adhesive without any expensive meter-mix dispensing equipment upgrades. Conclusion As the government regulations to reduce VOC emis- sions become more and more stringent, film-laminating converters are faced with several choices that enable them to comply with the new laws. Polyurethane disper- sions and acrylic emulsions are very viable alternatives to conventional solvent-based products; when they are reacted with crosslinkers such as polyfunctional aziri- dine or dispersible isocyanate, they have properties that often exceed the solvent-borne systems. In addition, third-generation solventless adhesives are an alterna- tive technology to dry-bond laminating that also enables a converter to meet the rapidly changing environmental and performance standards. About the Author Peter A. Voss is industry technical manager, Flexible Packaging Group, for H.B. Fuller Co., Vadnais Heights, MN. For more information about the new water- based adhesives, call H.B. Fuller Co. at 651-236-5629. Laminator Lamination Unwind Laminated Rewind Printed Unwind Print Unwind Print Rewind Central Impression Press Adhesive Applicator A flexo press with a separate laminator allows the converter to use both machines in tandem or independently, thus offering a wide variety of applications. Copyright Foundation of Flexographic Technical Association FLEXO Magazine