Novolac adhesives

Although unmodified phenolic novolac adhesives (particularly for tyre-cord bonding) can give bonds that exhibit both excellent thermal and environmental durability, they are also inherently brittle. To reduce the shrinkage on cure and to provide stress relief within the joint, novolacs can be co-cured with, particularly, acrylonitrile butadiene elastomers. 

Phenolic novolac adhesives are extensively used in Automotive applications bonding friction material to steel in the production of brakes, clutches and drive shafts. They are also used as tyre-cord adhesives and in the manufacture of furniture, laminated board and grinding wheels. See also Wood adhesives - phenolics. 

The use of primers. Primers are an essential component of some nitrile-phenolic and epoxy-novolac adhesives. They consist of solutions... 

Fig. 108. Delay times and creep of 1 cm overlap-shear joints at 75°C with epoxy-novolac adhesive (Bonded Structures Ltd) d = discontinued, f = faded (after Allen and Shanahan, 1976).

Fig. 122. Behaviour of an epoxy-novolac adhesive on extended exposure trial (data from Hockney, 1973).

Phenolic Resins. Phenohc resins (qv) are formed by the reaction of phenol [108-95-2] C H O, and formaldehyde [50-00-0] CH2O. If basic conditions and an excess of formaldehyde are used, the result is a resole phenohc resin, which will cure by itself Hberating water. If an acid catalyst and an excess of phenol are used, the result is a novolac phenohc resin, which is not self-curing. Novolac phenohc resins are typically formulated to contain a curing agent which is most often a material known as hexamethylenetetraamine [100-97-0] C H22N4. Phenohc resin adhesives are found in film or solution... 

Many applications of novolacs are found in the electronics industry. Examples include microchip module packaging, circuit board adhesives, and photoresists for microchip etching. These applications are very sensitive to trace metal contamination. Therefore the applicable novolacs have stringent metal-content specifications, often in the low ppb range. Low level restrictions may also be applied to free phenol, acid, moisture, and other monomers. There is often a strong interaction between the monomers and catalysts chosen and attainment of low metals levels. These requirements, in combination with the high temperature requirements mentioned above, often dictate special materials be used for reactor vessel construction. Whereas many resoles can be processed in mild steel reactors, novolacs require special alloys (e.g. Inconel ), titanium, or glass for contact surfaces. These materials are very expensive and most have associated maintenance problems as well. 

Resol resins thermoset on heating and are used for adhesives. Novolacs require a further source of formaldehyde in the form of hexamethylenetetramine to produce molding powders. Phenolic moldings are resistant to heat, chemicals, and moisture with good electrical and heat insulation qualities. Complex phenols from, e.g., cashew-nut shell liquid, are used in making brake... 

Linear novolac resins prepared by reacting para-alkylphenols with paraformaldehyde are of interest for adhesive tackifiers. As expected for step-growth polymerization, the molecular weights and viscosities of such oligomers prepared in one exemplary study increased as the ratio of formaldehyde to para-nonylphenol was increased from 0.32 to 1.00.21 As is usually the case, however, these reactions were not carried out to full conversion, and the measured Mn of an oligomer prepared with an equimolar phenol-to-formaldehyde ratio was 1400 g/mol. Plots of apparent shear viscosity versus shear rate of these p-nonylphenol novolac resins showed non-Newtonian rheological behavior. 

Phenolic novolacs, 18 760-761 Phenolic resin adhesives, 18 783-784 Phenolic resin can coatings, 18 38 Phenolic resin composites, 18 792-794 Phenolic resin drying-oil varnishes, 18 783 Phenolic resin fibers, 18 797-798 mechanical properties of, 18 798 Phenolic resin foam, 18 795-796 Phenolic resin manufacturers, U.S., 18 774 Phenolic resin polymerization, 18 760-765 alkaline catalysts in, 18 762-765 neutral catalysts in, 18 761-762 strong-acid catalysts in, 18 760-761 Phenolic resin prepregs, 18 793 Phenolic resin production unit, 18 766 Phenolic resins, 10 409 18 754-755, 756-802 22 10 26 763 in abrasive materials, 18 786-787 in air and oil filters, 18 790 additional reactants in, 18 759 analytical methods for, 18 774-779 applications of, 18 781-798 batch processes for, 18 766 from biomass and biochemical processes, 18 769-770... 

Optical Exposure. Multicomponent LB films were prepared from solutions of novolac/PAC varying in concentration from 5-50 wt% PAC, and transferred at 2.5 -10 dyn/cm. The films were composed of 15 - 20 monolayers, with an average film thickness of 30 nm, as measured by ellipsometry. Exposures were performed with a Canon FP-141 4 1 stepper (primarily g-line exposure) at an exposure setting of 5.2 and with a fine line test reticle that contains line/space patterns from 20 to 1 pm (40 to 2 pm pitch). They then were then developed in 0.1 - 0.2 M KOH, depending on the PAC content The wafers received a 20 min 120°C post development bake to improve adhesion to the Cr. Finally, the Cr was etched in Cyantek CR-14 chromium etchant, and the resist and Cr images were examined by SEM. 

Figure 17 provides an overview of the function of the diazoquinone/novolac materials. The matrix resin is a copolymer of a phenol and formaldehyde. The generic term for this class of polymers is novolac (18) meaning "new lacquer" and describes the purpose for which they were first developed. The chemical industry produces millions of tons of novolac each year where its end use is that of a thermoset resin and adhesive. Novolac is commonly used, for example, as the principle adhesive in the manufacture of plywood. 

It should be noted that the electrochemical measurements (corrosion potential and conductivity) for the two novolac epoxies cured with an aromatic amine from different sources showed good agreement, although the tensile adhesion and weight gain values were not as reproducible. 

Considering thermodynamics of adhesion, epoxy/novolac epoxy resins play a vital role for bonding applications especially for inhibition of composite propellants. In view of this fact, it is considered worthwhile to discuss the chemistry of epoxy/novolac epoxy resins in this section before we discuss other systems for this purpose. 

The inherent thermal stability of the phenol formaldehyde chemistry is preserved but with the crosslinking characteristics of the epoxy groups. However, epoxy novolacs also form very rigid and brittle polymers when fully cured because of their high crosslink density. For this reason, they are often used as modifiers in epoxy adhesive systems rather than as the base polymer. 

Many types of epoxy resins can be used in adhesive formulations. These are characterized in Table 4.1. The most commonly used type is the resin-based diglycidyl ether of bisphenol A (DGEB A). Epoxy novolac, flexible epoxy, high-functionality, and fihu-forming epoxy resins are also used in specialty applications. 

A general-purpose two-component adhesive that will provide high tensile shear strength up to 150°C is described in Table 12.11. The base epoxy resin in this formulation is a mixture of an epoxy novolac and a liquid DGEBA epoxy resin. 

TABLE 12.11 High-Temperature Epoxy Adhesive Utilizing Epoxy Novolac Resin14... 

The number of epoxide groups per molecule and the rigidity of the molecular structure are factors that affect the hot strength of the epoxy adhesive. Thus, epoxy novolac and gly-cidyl ethers of tetraphenolethane have become important resins for incorporating into high-temperature epoxy adhesives because of their multifunctionality. 

For maximum heat resistance, pyromellitic dianhydride is often used. The composition and properties of metal-to-metal adhesives based on a combination of epoxy novolac and a bisphenol A epoxy resin have been described in Sec. 12.5.1. Depending on the cure temperature and the choice of amine curing agent, strength as high as 3000 psi at room temperature and over 1000 psi in the range of-55 to + 150°C is possible. 

High-temperature epoxy adhesive utilizing epoxy novolac resin... 

Epoxy polymers (including epoxy novolacs) have been designed to meet most of these requirements and are almost universally used in such encap-sulant applications. Epoxy polymers exhibit superior adhesion that in many cases eliminates the need for a barrier or junction coating. They have a low coefScient of thermal expansion low shrinkage and low injection velocity, which means that low transfer or injection pressures can be used. These polymers also possess excellent mechanical properties coupled with low moisture and gas permeability. Above all, they are cheap and readily available. Other transfer-molding materials used to a limited extent include silicones, phenolic materials, and even polyesters. Most molding formulations are highly filled (70-75%) with materials such as quartz, fused silica, short... 

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