Urethane Adhesive Systems

Blocked isocyanate prepolymers have been mixed with epoxy resins and cured with amines.18,19 These blocked prepolymers will initially react with the amines to form amine-terminated prepolymers that crosslink the epoxy resin. Urethane amines are also offered commercially for use with epoxy resins to develop hybrid adhesive systems.20... 

Nearly all polymeric materials (including adhesives and sealants) shrink during solidification. Sometimes they shrink because of escaping solvent, leaving less mass in the bond line. Even 100 percent reactive adhesives, such as epoxies and urethanes, experience some shrinkage because their solid polymerized mass occupies less volume than the liquid reactants. Table 3.6 shows typical percentage cure shrinkage for various reactive adhesive systems. 

Several hybrid epoxy emulsions have been commercially prepared. An epoxy emulsion blended with waterborne aliphatic urethanes exhibited peel strength on aluminum of 10 lb/in—1.5 times greater than with the polyurethane itself. The optimum concentration of urethane in the final emulsion was about 50 percent by weight.13 Epoxy-phenolic dispersions have also been developed to provide waterborne adhesive systems with high glass transition temperature and chemical resistance. 

Many epoxy dispersions are compatible with most types of latex emulsions including acrylic, urethane, styrene butadiene, vinyl chloride, and polyvinyl acetate. The epoxy dispersion can be used as a modifier for these emulsions to alter handling and application characteristics such as emulsion rheology, foaming tendencies, pH sensitivity, wetting properties, and coating coalescence. They can also be reacted into the latex resin either by reacting the epoxy with a functionalized latex or by use of an epoxy with a coreactant. In this way adhesive systems can be formulated that are cured at room or elevated temperatures. 

Adhesives commonly used on thermosetting materials include epoxies, urethanes, cyanoacrylates, thermosetting acrylics, and a variety of nonstructural adhesive systems. The following discussion includes a very brief description of various thermosetting substrate materials, the properties that are critical relative to epoxy adhesion, and any special processes that should be noted for the particular substrate. 

Substrate cleaning usually involves the light sanding of a clean, dry bonding surface. A primer (urethane or silane) is sometimes used to improve adhesion. Urethanes are generally bonded with a flexible epoxy or a urethane adhesive system. 

When solvent welding or thermal welding is not practical or desired, adhesive systems can be used. Adhesive types such as epoxies, urethanes, thermosetting acrylics, nitrile phe-nolics, and cyanoacrylates permit ABS to be bonded to itself and to other substrates. The best adhesives have shown strength greater than that of ABS however, these adhesives provide very rigid bonds. 

Paste adhesives are supplied as either one- or two-component adhesive systems. They can be used in applications where pressure cannot be applied. Some two-part pastes cure at room temperature after the appropriate proportions are mixed. Epoxy, urethane, and acrylic adhesives are all available as paste adhesives. 

ZDEC is used in the following applications as a fast primary or secondary vulcanization accelerator in NR, SBR, IIR, EPDM and for natural and synthetic latex a stabilizer in butyl, butadiene, and urethane rubbers an antioxidant in rubber-based adhesive systems a stabilizer in cement a heat stabilizer for polyethylene. 

Over the last four decades there have been a number of attempts to wed the unique benefits of polyurethane adhesives with the benefits of other adhesive systems. These attempts have led to the reporting of a variety of urethane hybrids. Early work focused on simple blends for example, in 1964 Union Carbide blended organic isocyanates with ethylene-vinyl acetate copolymers [66]. These blends were used as an adhesive interlayer in glass laminations, particularly safety glass laminates. Similarly, polylurethane poxy blends for safety glass laminates were reported in 1970 [67]. 

More recent efforts have focused on developments that create true hybrids. For example, blocked isocyanate prepolymers have been mixed with epoxy resins and cured with amines [68-70]. These blocked prepolymers will react initially with the amines to form amine-terminated prepolymers that cross-link the epoxy resin. Several blocked isocyanates are commercially available. The DESMOCAP (Bayer) llA and 12A products are isocyanates (believed to be blocked with nonylphenol) used as flexibilizing agents for epoxy resins. ANCAREZ (trademark. Pacific Anchor, Inc.) 2150 is a blocked isocyanate epoxy blend used as an adhesion promoter for vinyl plastisols. A one-package, heat-cured hybrid adhesive was reported consisting of isophorone diisocyanate, epoxy resin, and a dispersed solid curative based on the salt of ethylenediamine and bisphenol A [71]. Urethane amines are offered commercially that can be used with epoxy resins to develop hybrid adhesive systems [72]. 

Uses Polyester for coil coatings, appliance coatings, adhesives, blocked urethane systems... 

Malofsky and Baccei, from the Loctite Corporation, report on the significant mechanical property improvements obtained with maleimide and nadic capped monomers and prepolymers as additives in anaerobic methacrylate/ acrylate adhesive systems. Significant improvement in thermal resistance was noted in a PEGMA (polyethyleneglycol diroethacrylate) system in which a polymerizable maleimide addition was incorporated. A "neat" polymerized urethane methacrylate failed catastrophically within 1000 hrs. at... 

Product Information Tyrite 7500A Urethane Structural Adhesive System, Lord Corp., Industrial Adhesives Division, 2000 West Grandview Blvd., PO Box 10038, Erie, PA 16514 (July 10, 1984). 

Reactive acrylics are differentiated from other two-component adhesive systems snch as epoxies or urethanes by the fact that the cure is catalytic, is relatively insensitive to the amount of catalyst used, and is not dependent npon mixing precise stoichiometric amounts of adhesive and catalyst. An important development was the commercialisation of a highly pnrified form of dihydropyridine activator which contains 85-90% of the key active ingredient 3,5-diethyl-l,2-dihydro-l-phenyl-2-propylpyridine ... 

Method D appears to be possibly the most important type of isocyanate-based adhesive system. It is similar to Method B in that a preformed, fully reacted, high molecular weight polymer is employed as a vehicle in the adhesive formulation. The strength of the vehicle holds adherend members in exact position after assembly until the full bond has formed. Method D differs from Method B in that its vehicle polymer is a polyurethane. A further difference is that the inherent adhesive character and strength of the polyurethane vehicle frequently enables its use without added di- or poiyisocyanate. This strength may be realized in essentially amorphous compositions such as the thermoplastic polyurethane elastomers or millable gums. Or it may be achieved with crystallizing urethane adhesive polymers. 

Ex. 7. Bostik 7070 (100 parts) with Boscodur No. 1 (5 parts) appears to be another example of a two part millable polyurethane gum adhesive system. It is recommended by the manufacturer as a laundering and dry cleaning resistant cement for bonding urethane sponge and urethane rubber. It is also recom-... 

Ex. 1. Tuftane film is ideally suited for bonding emblems, numerals, and letters to many fabrics by heat and pressure alone. It also flame-bonds well to both polyester- and polyether-urethane foams at commercial bonding speeds. Since it contains no volatiles it does not require cure times as do solvent- or water-based adhesive systems. All Tuftane films can be adhered thermally by hot bar, thermal impulse, ultrasonic, or dielectric methods over a wide range of temperatures. Adhesive lamination to many substrates is possible by the heated drum, curing oven, or multiple can methods. Fabric bonds made with Tuftane are strong and withstand laundering and dry cleaning. 

Paint systems differ in their cure chemistry and ingredient content, such as melamine, polyester, acrylic, urethane, etc. Some work has been done on determining the results with different paint systems (urethane versus melamine) or similar paint systems from different suppliers, but certainly not as extensive as the work that has been done with adhesion promoter and paint systems on TPOs. In gen-... 

Phenol-formaldehyde Resorcinol-formaldehyde Resorcinol + hexamethylenetetramine SiOj + resorcinol + hexamethylenetetramine Commercial adhesive systems based on acrylics, epoxydes, urethanes or cyanocrylates technologies Bi-functional silanes bis(triethoxysilylpropyl)tetrasu]fane (TESPT)... 

Usage of phosphoms-based flame retardants for 1994 in the United States has been projected to be 150 million (168). The largest volume use maybe in plasticized vinyl. Other use areas for phosphoms flame retardants are flexible urethane foams, polyester resins and other thermoset resins, adhesives, textiles, polycarbonate—ABS blends, and some other thermoplastics. Development efforts are well advanced to find appHcations for phosphoms flame retardants, especially ammonium polyphosphate combinations, in polyolefins, and red phosphoms in nylons. Interest is strong in finding phosphoms-based alternatives to those halogen-containing systems which have encountered environmental opposition, especially in Europe. 

T Urethanes not shown because of great differences in physical properties, depending on formulations. Adhesion characteristics should he related by actual test data. Any system which shows concrete failure when tested for surfacing adhesion should he rated excellent with decreasing rating for systems showing failure in cohesion or adhesion below concrete failure. 

Almost all urethane materials are synthesized without the use of solvents or water as diluents or earners and are referred to as being 100% solids. This is true of all foams and elastomers. There are many products, however, which do utilize solvents or water, and these are known as solvent-borne and waterborne systems, respectively. In the past, many coatings, adhesives, and binders were formulated using a solvent to reduce viscosity and/or ease application. However, the use of volatile solvents has been dramatically curtailed in favor of more environmentally friendly water (see Section 4.1.3), and now there are many aqueous coatings, adhesives, and associated raw materials. Hydrophilic raw materials capable of being dispersed in water are called water reducible (or water dispersible), meaning they are sufficiently hydrophilic so as to be readily emulsified in water to form stable colloidal dispersions. 

---