Adhesives formulations

Tetrahydrofurfuryl alcohol is used in elastomer production. As a solvent for the polymerization initiator, it finds appHcation in the manufacture of chlorohydrin mbber. Additionally, tetrahydrofurfuryl alcohol is used as a catalyst solvent-activator and reactive diluent in epoxy formulations for a variety of apphcations. Where exceptional moisture resistance is needed, as for outdoor appHcations, furfuryl alcohol is used jointly with tetrahydrofurfuryl alcohol in epoxy adhesive formulations. 

As succeeding panels are laid-up, a stack of panels is formed. If the panels are to be cold-pressed, an uncommon procedure in modern manufacturing, the stack will be high enough to fit into the cold-press. The stack is roUed into the press, the press is closed under hydraulic pressure and the bonding pressure, 1035—1205 (ca 150—175 psi) is maintained for the time requited to form a bond. This time could vary from 30 to 120 minutes, depending on temperature and the adhesive formulation used. 

Adhesives. Acryhc emulsion and solution polymers form the basis of a variety of adhesive types. The principal use is in pressure-sensitive adhesives, where a film of a very low T (<—20 " C) acrylic polymer or copolymer is used on the adherent side of tapes, decals, and labels. Acrylics provide a good balance of tack and bond strength with exceptional color stabiUty and resistance to aging (201,202). AcryUcs also find use in numerous types of constmction adhesive formulations and as film-to-film laminating adhesives (qv). 

Although the anionic polymerization mechanism is the predominant one for the cyanoacryhc esters, the monomer will polymerize free-radically under prolonged exposure to heat or light. To extend the usable shelf life, free-radical stabilizers such as quinones or hindered phenols are a necessary part of the adhesive formulation. 

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

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. 

The paster is a nonheated operation. The most common paster adhesive formulation consists of poly(vinyl alcohol)—clay—starch blends (10). A 100% area adhesive coverage is used. The rate of bond strength development of the adhesive is an important commercial concern and rapid bond formation rates are desirable. 

Adhesives. High concentration (>10%) solutions of poly(ethylene oxide) exhibit wet tack properties that are used in several adhesive appHcations. The tackiness disappears when the polymer dries and this property can be successfully utilized in appHcations that require adhesion only in moist conditions. PEO is also known to form solution complexes with several phenoHc and phenoxy resins. Solution blends of PEO and phenoxy resins are known to exhibit synergistic effects, leading to high adhesion strength on aluminum surfaces. Adhesive formulations are available from the manufacturers. 

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). 

Adhesives. Clays, especially kaolin and attapulgite, are widely used in various adhesive formulations. Adhesives (qv) containing clays can be derived from natural products such as starch or protein, or be whoUy synthetic, eg, latex, hot melt, emulsion, etc. 

Dicyandiamide fluidifies various adhesives and glues. In the presence of dicyandiamide, the initial viscosity of the adhesive formulations is lowered and maintained at a lower range for longer periods of time, thus preventing premature gelling and extending the useful life of the adhesive (see Adhesives). 

Compounding is quite different for the two systems. The solvent base system is dependent on magnesium oxide and a /-butylphenoHc resin in the formulation to provide specific adhesion, tack, and added strength. Neither of these materials have proven useful in latex adhesive formulations due to colloidal incompatibihty. In addition, 2inc oxide slowly reacts with carboxylated latexes and reduces their tack. Zinc oxide is an acceptable additive to anionic latex, however. Other tackifying resins, such as rosin acids and esters, must be used with anionic latexes to provide sufficient tack and open time. 

It also finds miscellaneous applications in textile and metal coatings and in adhesive formulations. Where it is to be used as a safety glass interleaver, a very pure product is required and this is most conveniently prepared from... 

Tertiary amines form a further important class of catalytic hardeners. For example, triethylamine has found use in adhesive formulations. Also of value are the aromatic substituted tertiary amines such as benzyldimethylamine and dimethyldiaminophenol. They have found uses in adhesive and coating applications. A long pot life may be achieved by the use of salts of the aromatic substituted amines. 

The epoxidised oils are seldom used in a cross-linked form as the products are rather soft and leathery. Exceptions to this are their occasional use as diluents for more viscous resins and some applications in adhesive formulations. 

In developing criteria for the ranking of adhesive formulations or adherend surface treatments or primers, it is necessary to distinguish between two different situations. In one case (contact adhesion), a true interface is believed to exist across which intermolecular forces are engaged, while in the other, an interphase is formed by diffusive interpenetration or interdigitation between the adhesive and the adherend (diffusion interphase adhesion). Even in the case of contact adhesion, more often than not, an mi vphase of macroscopic thickness forms on... 

Some rubber base adhesives need vulcanization to produce adequate ultimate strength. The adhesion is mainly due to chemical interactions at the interface. Other rubber base adhesives (contact adhesives) do not necessarily need vulcanization but rather adequate formulation to produce adhesive joints, mainly with porous substrates. In this case, the mechanism of diffusion dominates their adhesion properties. Consequently, the properties of the elastomeric adhesives depend on both the variety of intrinsic properties in natural and synthetic elastomers, and the modifying additives which may be incorporated into the adhesive formulation (tackifiers, reinforcing resins, fillers, plasticizers, curing agents, etc.). 

The NBR used in adhesive formulations is obtained by emulsion polymeriza-... 

Tackifiers and modifiers are generally added to improve the adhesive performance of synthetic elastomers. All resins added to an adhesive formulation modify their properties (viscosity, open time, tack) and therefore these resins are also called... 

Salt formation. The resin acids have a low acid strength. The pa s (ionization constants) values of resin acids are difficult to obtain, and values of 6.4 and 5.7 have been reported [23] for abietic and dehydroabietic acids, respectively. Resin acids form salts with sodium and aluminium. These salts can be used in detergents because of micelle formation at low concentrations. Other metal salts (resinates) of magnesium, barium, calcium, lead, zinc and cobalt are used in inks and adhesive formulations. These resinates are prepared by precipitation (addition of the heavy metal salt to a solution of sodium resinate) or fusion (rosin is fused with the heavy metal compound). 

Colour. The colour of resins ranges from water-white to dark brown. Colour may be an important factor in resin choice depending on end use. Pale colours are necessary in some types of adhesives, whereas darker colours may be tolerated in rubber formulations, especially where carbon black filler is incorporated. Medium-coloured resins can be used in most adhesive formulations. 

For rosins and rosin esters, the produets having high aeid numbers are the most susceptible to oxidation and have inferior viscosity stability and colour stability in adhesive formulations. Thus, when stability properties are essential in adhesives, rosin esters rather than high aeid number rosins are used. However, the high acid number resins are polar and display better adhesion to polar elastomers and polymeric surfaces. 

In general, fully compatible resin are desirable. However, there are many applications where borderline compatibility is tolerated, and even in some cases, borderline compatibility or controlled incompatibility may enhance tack in adhesive systems. On the other hand, a resin with a borderline compatibility in combination with an oil or plasticizer in an adhesive formulation, will result in phase separation and therefore the migration of the oil or plasticizer to the adhesive surface is favoured. 

Plasticizers can be classified according to their chemical nature. The most important classes of plasticizers used in rubber adhesives are phthalates, polymeric plasticizers, and esters. The group phthalate plasticizers constitutes the biggest and most widely used plasticizers. The linear alkyl phthalates impart improved low-temperature performance and have reduced volatility. Most of the polymeric plasticizers are saturated polyesters obtained by reaction of a diol with a dicarboxylic acid. The most common diols are propanediol, 1,3- and 1,4-butanediol, and 1,6-hexanediol. Adipic, phthalic and sebacic acids are common carboxylic acids used in the manufacture of polymeric plasticizers. Some poly-hydroxybutyrates are used in rubber adhesive formulations. Both the molecular weight and the chemical nature determine the performance of the polymeric plasticizers. Increasing the molecular weight reduces the volatility of the plasticizer but reduces the plasticizing efficiency and low-temperature properties. Typical esters used as plasticizers are n-butyl acetate and cellulose acetobutyrate. 

Plasticizers reduce hardness, enhance tack and reduce cost in rubber base adhesive formulations. A plasticizer must be easily miscible and highly compatible with other ingredients in the formulations and with the surfaces to which the adhesive is applied. The compatibility and miscibility of plasticizers can be estimated from the solubility parameter values. Most of plasticizers have solubility parameters ranging between 8.5 and 10.5 hildebrands. However, the high miscibility and compatibility also lead to easier diffusion of the plasticizer to the surface, decreasing the adhesion properties. Therefore, plasticizers should be carefully selected and generally combinations of two or more of them are used. 

Density. Most fillers added in rubber base formulation have a density between 2 and 2.7 g/cm-, except barium sulphate (4-4.9 g/cm- ) and zinc oxide (5.6 g/cm ). Addition of filler increases the free volume of the polymer and, in general, there is a critical concentration of filler at which the density of the formulation increases. The method of incorporation of filler in the adhesive formulation is important because air voids may appear when a poor dispersion is produced. 

Clay and talc are the most common fillers in rubber base adhesive formulations. Both have platy shapes favouring the interactions with elastomers. 

Aromatic amines are the most effective primary antioxidants (Fig. 34) but they are discolouring and can only be used where the darker colours are acceptable (for instance in rubber adhesive formulations containing carbon blacks as fillers). The... 

Acid acceptor. This is the main function of metal oxides in CR adhesive formulations. Upon age, small amounts of hydrochloric acid are released which may cause discolouration and substrate degradation. Magnesium oxide (4 phr) and zinc oxide (5 phr) act synergistically in the stabilization of solvent-borne polychloroprene adhesives against dehydrochlorination. 

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