Adhesives, hot melt

Hot-Melt Adhesives. Hot-melt adhesives are 100% nonvolatile thermoplastic materials that can be heated to a melt and then appHed as a hquid to an adherend. The bond is formed when the adhesive resolidifies. The oldest example of a hot-melt adhesive is sealing wax. 

Formulations. Hot-melt adhesive formulation involves providing the best physical properties over as large a temperature range as possible. 

This type of adhesive is generally useful in the temperature range where the material is either leathery or mbbery, ie, between the glass-transition temperature and the melt temperature. Hot-melt adhesives are based on thermoplastic polymers that may be compounded or uncompounded ethylene—vinyl acetate copolymers, paraffin waxes, polypropylene, phenoxy resins, styrene—butadiene copolymers, ethylene—ethyl acrylate copolymers, and low, and low density polypropylene are used in the compounded state polyesters, polyamides, and polyurethanes are used in the mosdy uncompounded state. 

In the area of moleculady designed hot-melt adhesives, the most widely used resins are the polyamides (qv), formed upon reaction of a diamine and a dimer acid. Dimer acids (qv) are obtained from the Diels-Alder reaction of unsaturated fatty acids. Linoleic acid is an example. Judicious selection of diamine and diacid leads to a wide range of adhesive properties. Typical shear characteristics are in the range of thousands of kilopascals and are dependent upon temperature. Although hot-melt adhesives normally become quite brittle below the glass-transition temperature, these materials can often attain physical properties that approach those of a stmctural adhesive. These properties severely degrade as the material becomes Hquid above the melt temperature. 

Pentaerythritol in rosin ester form is used in hot-melt adhesive formulations, especially ethylene—vinyl acetate (EVA) copolymers, as a tackifier. Polyethers of pentaerythritol or trim ethyl ol eth an e are also used in EVA and polyurethane adhesives, which exhibit excellent bond strength and water resistance. The adhesives maybe available as EVA melts or dispersions (90,91) or as thixotropic, one-package, curable polyurethanes (92). Pentaerythritol spko ortho esters have been used in epoxy resin adhesives (93). The EVA adhesives are especially suitable for cellulose (paper, etc) bonding. 

A number of chemical products are derived from Sasol s synthetic fuel operations based on the Fischer-Tropsch synthesis including paraffin waxes from the Arge process and several polar and nonpolar hydrocarbon mixtures from the Synthol process. Products suitable for use as hot melt adhesives, PVC lubricants, cormgated cardboard coating emulsions, and poHshes have been developed from Arge waxes. Wax blends containing medium and hard wax fractions are useful for making candles, and over 20,000 t/yr of wax are sold for this appHcation. 

Polyimides of 6FDA and aUphatic diamines with good low temperature processkig and low moisture swelling are known to be useful as hot-melt adhesives (109). Aluminum strips bonded by this polymer (177°C/172 kPa (25 psi) for 15 min) exhibited a lap-shear strength of 53 MPa (7690 psi) at room temperature and 35 MPa (5090 psi) at 100°C. The heat- and moisture-resistant 6F-containing Pis useful ki electronic devices are prepared from... 

In order to increase the solubiUty parameter of CPD-based resins, vinyl aromatic compounds, as well as other polar monomers, have been copolymerized with CPD. Indene and styrene are two common aromatic streams used to modify cyclodiene-based resins. They may be used as pure monomers or contained in aromatic steam cracked petroleum fractions. Addition of indene at the expense of DCPD in a thermal polymerization has been found to lower the yield and softening point of the resin (55). CompatibiUty of a resin with ethylene—vinyl acetate (EVA) copolymers, which are used in hot melt adhesive appHcations, may be improved by the copolymerization of aromatic monomers with CPD. As with other thermally polymerized CPD-based resins, aromatic modified thermal resins may be hydrogenated. 

Heteroatom functionalized terpene resins are also utilized in hot melt adhesive and ink appHcations. Diels-Alder reaction of terpenic dienes or trienes with acrylates, methacrylates, or other a, P-unsaturated esters of polyhydric alcohols has been shown to yield resins with superior pressure sensitive adhesive properties relative to petroleum and unmodified polyterpene resins (107). Limonene—phenol resins, produced by the BF etherate-catalyzed condensation of 1.4—2.0 moles of limonene with 1.0 mole of phenol have been shown to impart improved tack, elongation, and tensile strength to ethylene—vinyl acetate and ethylene—methyl acrylate-based hot melt adhesive systems (108). Terpene polyol ethers have been shown to be particularly effective tackifiers in pressure sensitive adhesive appHcations (109). 

Styrenic block copolymers (SBCs) are also widely used in HMA and PSA appHcations. Most hot melt appHed pressure sensitive adhesives are based on triblock copolymers consisting of SIS or SBS combinations (S = styrene, I = isoprene B = butadiene). Pressure sensitive adhesives typically employ low styrene, high molecular weight SIS polymers while hot melt adhesives usually use higher styrene, lower molecular weight SBCs. Resins compatible with the mid-block of an SBC improves tack properties those compatible with the end blocks control melt viscosity and temperature performance. 

Poly(viayl acetate) emulsions or hot-melt adhesives are typically used to form the manufacturer s or glue lap joiat of the box. The main criteria for the adhesive is that it provide a strong and tough final bond and that it set up quickly enough to allow fast box production speeds. Production rates ia excess of 240 boxes per minute are not uncommon ia the iadustry. 

The adhesives (qv) used to form tube seams and bag bottoms include unborated dextrin, borated dextrin, casein, latex—casein, latex, poly(vinyl acetate), vinyl acetate copolymers, and hot-melt materials (10,27). Dextrin and casein adhesives are more commonly used in the production of grocery sacks vinyl acetate-type adhesives are commonly used in ah paper multiwah bags. The hot-melt adhesives are typicahy used to tack the phes of the multiwah bag together and to form the seam and bottom joints when polymer film phes or coated paper phes are used in bag constmction. 

The seam closure on a folding carton is typicahy made using a latex, poly(vinyl acetate), vinyl acetate copolymer, or hot-melt adhesive (27). The choice of adhesive depends on a number of factors, including the nature of any coating used on the package and the production speeds required. 

Dispersion at temperatures of 90—110°C is a common final step io European mills processiog wax-coated old cormgated containers. Dispersion temperatures less than 90°C are reported to reduce wax particle size to improve pulp drainage properties on paper machines while improving paper strength (45). Dispersion has been used to reduce hot-melt adhesive, plastic coating, and asphalt particle size. These low density particles can then be removed from the pulp by flotation (46). 

Rosin, modified rosins, and derivatives are used in hot-melt adhesives. They are based primarily on ethylene—vinyl acetate copolymers. The rosin derivative is used in approximately a 1 1 1 concentration with the polymer and a wax. The resin provides specific adhesion to the substrates and reduces the viscosity at elevated temperatures, allowing the adhesive to be appHed as a molten material. 

OC-Methylstyrene. This compound is not a styrenic monomer in the strict sense. The methyl substitution on the side chain, rather than the aromatic ring, moderates its reactivity in polymerization. It is used as a specialty monomer in ABS resins, coatings, polyester resins, and hot-melt adhesives. As a copolymer in ABS and polystyrene, it increases the heat-distortion resistance of the product. In coatings and resins, it moderates reaction rates and improves clarity. Physical properties of a-methylstyrene [98-83-9] are shown in Table 12. 

Uses ndReactions. Some of the principal uses for P-pinene are for manufacturing terpene resins and for thermal isomerization (pyrolysis) to myrcene. The resins are made by Lewis acid (usuaUy AlCl ) polymerization of P-pinene, either as a homopolymer or as a copolymer with other terpenes such as limonene. P-Pinene polymerizes much easier than a-pinene and the resins are usehil in pressure-sensitive adhesives, hot-melt adhesives and coatings, and elastomeric sealants. One of the first syntheses of a new fragrance chemical from turpentine sources used formaldehyde with P-pinene in a Prins reaction to produce the alcohol, Nopol (26) (59). 

Polyurethane adhesives are known for excellent adhesion, flexibihty, toughness, high cohesive strength, and fast cure rates. Polyurethane adhesives rely on the curing of multifunctional isocyanate-terrninated prepolymers with moisture or on the reaction with the substrate, eg, wood and ceUulosic fibers. Two-component adhesives consist of an isocyanate prepolymer, which is cured with low equivalent weight diols, polyols, diamines, or polyamines. Such systems can be used neat or as solution. The two components are kept separately before apphcation. Two-component polyurethane systems are also used as hot-melt adhesives. 

Other apphcations for VP/VA copolymers are uses as water-soluble or remoistenable hot melt adhesives (140), pharmaceutical tablet coatings, binders, and controUed-release substrates. 

Differences among the processes have a major impact on the use of the products. Products from a particular process or manufacturer may dominate one market, while products from a different process may be preferred in a different appHcation. Major uses include hot-melt adhesives for appHcations requiring high temperature performance, additives to improve the processing of plastics, sHp and mb additives for inks and paints, and cosmetic appHcations. 

DistHlation is then used to separate the hydrocarbons into different products, including Hquid fuels and waxes with melting points ranging from about 45—106°C. Currently the waxes are produced in large volumes in South Africa and Malaysia, with an estimated 12,000—14,000 t consumed in the United States in 1994. Uses are similar to those for polyethylene waxes, including hot-melt adhesives and additives for inks and coatings. 

Low viscosity cellulose propionate butyrate esters containing 3—5% butyryl, 40—50% propionyl, and 2—3% hydroxyl groups have excellent compatibihty with oil-modified alkyd resins (qv) and are used in wood furniture coatings (155). Acetate butyrate esters have been used in such varied apphcations as hot-melt adhesive formulations (156), electrostatically spray-coated powders for fusible, non-cratering coatings on metal surfaces (157—159), contact lenses (qv) with improved oxygen permeabiUty and excellent wear characteristics (160—162), and as reverse-osmosis membranes for desalination of water (163). 

Lamination. la lamination a film is prepared by caleaderiag or extmsioa (see Laminated materials, plastic). It is thea adhered to a textile at a laminator by either an adhesive or sufficient heat which partially melts the film to obtain a mechanical bond. There are a variety of adhesives available for lamination, including solvent systems, water-base latex systems, and various forms of hot melt adhesives (qv). 

Polyamide Resins. Another class of polyamide resins, in addition to the Hquid resins used as epoxy hardeners, are the thermoplastic type, prepared generaHy by the condensation reaction of polyamines with polybasic fatty acids. These resins find use in certain hot-melt adhesives, coatings, and inks. Diamines, typicaHy EDA (233), are the principal amine reactant however, tri- and tetramines are sometimes used at low levels to achieve specific performance. 

Formerly Mobay. Includes some polymers with aUphatic polycarbonate segments (trade named Desmopan). For hot-melt adhesives. 

Some grades of polyurethane and polyester copolymers are used as hot-melt adhesives. AppHcations include shoe manufacture and as an adhesive interlayer in coextmsion. 

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