Novolac application

Coating system - Epoxy novolac Application date - 1995 and on-going... 

The composition of an epoxide moulding material will greatly depend on the specific application, and this has been discussed at length. ". The resin may be of the epoxide novolac type and there will also be present hardeners, fillers (such as silica), a silane coupling agent, pigment, flame retardant and a wax release agent. 

It is traditional to divide phenolics into two main categories. These are novolacs and resoles. This system of classification is consistent with the division of applications as well as the compositions and conditions of resin manufacture. Novolacs are used primarily in the molding industries and electronics applications. Resoles are used primarily as binders for other materials. 

While resoles account for most of the volume in phenolic products, novolacs account for most of the diversity. They are used in a wide variety of applications. They also tend to be significantly more expensive than resoles. The higher cost and pricing structure permits more creativity in their formulation. Many novolacs are made in small volumes and are formulated for very specific purposes. It is, therefore, rather difficult to make meaningful generalizations about novolacs beyond a few basic concepts. 

While phenol is the most common monomer for novolac manufacture, it is far more common to see incorporation of other phenolic materials with novolacs than with resoles. Cresols, xylenols, resorcinol, catechols, bisphenols, and a variety of phenols with longer alkyl side chains are often used. While most resoles are made with a single phenolic monomer, two or more phenolic materials are often seen in novolac formulae. These additional monomers may be needed to impart special flow characteristics under heat, change a glass transition temperature, modify cure speed, or to adjust solubility in the application process among others. 

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. 

An example of a novolac formula is presented in Table 8. A resin of this type might be used to manufacture electronics composites. Formulae for other applications might show considerable differences in molar ratio, monomer choice. 

Cured phenolics are universally brittle in nature. This is true of both resoles and novolacs and does not depend much on the source of methylene used to promote cure. Consequently, the fillers used in molded articles are highly important to the design of the manufactured product. With resoles, the fiber or filler are usually the primary component of the final composite, with the resole acting as a binder or impregnating agent. With novolacs the resin may be the major component in the molded part. Poly-silanes and other organic polymers are also added in some applications to promote impact resistance and toughness [192]. 

The literature on basic- and acid-catalyzed alkylation of phenol and of its derivatives is wide [1,2], since this class of reactions finds industrial application for the synthesis of several intermediates 2-methylphenol as a monomer for the synthesis of epoxy cresol novolac resin 2,5-dimethylphenol as an intermediate for the synthesis of antiseptics, dyes and antioxidants 2,6-dimethylphenol used for the manufacture of polyphenylenoxide resins, and 2,3,6-trimethylphenol as a starting material for the synthesis of vitamin E. The nature of the products obtained in phenol methylation is affected by the surface characteristics of the catalyst, since catalysts having acid features address the electrophilic substitution in the ortho and para positions with respect to the hydroxy group (steric effects in confined environments may however affect the ortho/para-C-alkylation ratio), while with basic catalysts the ortho positions become the... 

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... 

While "conventional positive photoresists" are sensitive, high-resolution materials, they are essentially opaque to radiation below 300 nm. This has led researchers to examine alternate chemistry for deep-UV applications. Examples of deep-UV sensitive dissolution inhibitors include aliphatic diazoketones (61-64) and nitrobenzyl esters (65). Certain onium salts have also recently been shown to be effective inhibitors for phenolic resins (66). A novel e-beam sensitive dissolution inhibition resist was designed by Bowden, et al a (67) based on the use of a novolac resin with a poly(olefin sulfone) dissolution inhibitor. The aqueous, base-soluble novolac is rendered less soluble via addition of -10 wt % poly(2-methyl pentene-1 sulfone)(PMPS). Irradiation causes main chain scission of PMPS followed by depolymerization to volatile monomers (68). The dissolution inhibitor is thus effectively "vaporized", restoring solubility in aqueous base to the irradiated portions of the resist. Alternate resist systems based on this chemistry have also been reported (69,70). 

Interest in solution inhibition resist systems is not limited to photoresist technology. Systems that are sensitive to electron-beam irradiation have also been of active interest. While conventional positive photoresists may be used for e-beam applications (31,32), they exhibit poor sensitivity and alternatives are desirable. Bowden, et al, at AT T Bell Laboratories, developed a novel, novolac-poly(2-methyl-l-pentene sulfone) (PMPS) composite resist, NPR (Figure 9) (33,34). PMPS, which acts as a dissolution inhibitor for the novolac resin, undergoes spontaneous depolymerization upon irradiation (35). Subsequent vaporization facilitates aqueous base removal of the exposed regions. Resist systems based on this chemistry have also been reported by other workers (36,37). 

BPF isomers (Novolac) may arise from their application in the manufacture of Novolac glycidyl ethers (NOGE), which serve as scavengers for hydrogen chloride in PVC organosol coatings. 

The positive resist materials evolved from discoveries made by the Kalle Corporation in Germany who developed the first positive-acting photoresist based on the use of a novolac matrix resin and a diazoquinone photoactive compound or sensitizer. The original materials were designed to produce photoplates used in the printing industry. These same materials have been adopted by semi-conductor fabrication engineers and continue to function effectively in that more demanding application. 

A collapsible mandrel is prepared by applying a very thin coat of silicone grease on it followed by application of aluminum foil of suitable thickness. This prepared mandrel is then held in the lathe machine. A thin uniform coat of resin (novolac epoxy resin plus hardener) is applied to the prepared collapsible mandrel revolving at a speed of 40 rpm and is allowed to cure partially. Then the dried rayon thread on a spool is passed through the resin formulation and is wound on to the mandrel... 

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. 

DNQ—novolac resist chemistry has proved to have remarkable flexibility and extendibility. First introduced for printing applications, DNQ—novolac resists have been available since the eady 1960s in formulations intended for electronics applications. At present, most semiconductor manufacturing processes employ this resist chemistry. Careful contemporary research and engineering support the continuing refinement of this family of materials. 

One final example of the application of onium salt photochemistry in positive resist materials should be mentioned, because it does not include any postexposure acid-catalyzed processes and therefore does not encompass the principle of chemical amplification (79). Interestingly, Newman (79) has determined that onium salts themselves can inhibit the dissolution of novolac in aqueous base and that irradiation of such an onium salt-novolac resist restores the solubility of the resin in developer and leads to a positive-tone image. In this application, the onium salt behaves like diazonaphthoquinone in a typical positive resist. Recently, Ito (80) has reported also the use of onium salts as novolac dissolution inhibitors. 

DNQ-novolac positive resists have been used also with e-beam exposure. The 2,1,4 DNQ isomers give superior performance in these applications (101). The e-beam sensitivity of these materials is 40 xC/cm2. 

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