Epoxy cresol novolac curing

Biernath et al. concluded that phenolic novolac and epoxidized cresol novolac cure reactions using triphenylphosphine as the catalyst had a short initiation period wherein the concentration of phenolate ion increased, followed by a (steady-state) propagation regime where the number of reactive phenolate species was constant.85 The epoxy ring opening was reportedly first order in the steady-state regime. 

R. W. Biemath and D. S. Soane, Cure Kinetics of Epoxy Cresol Novolac Encap-sulant for Microelectronic Packaging, in Contemporary Topic in Polymer Science. Advances in New Material. Vol. 7, J. S. Salamone and J. S. Riffle (Eds.), Plenum, New York, 1992, pp. 103-160. 

All samples were prepared from a commercially available epoxy cresol novolac-phenol formaldehyde novolac-tertia-ry amine based molding compound. Pelletized preforms were heated to 85°C in a RF preheater prior to being transfer molded at 180°C/68 atm. for 90 sec. Molded samples were cooled in air to room temperature and stored in a desiccated environment until testing or subsequent thermal treatment. Post mold curing, PMC, was accomplished in a gravity oven at 175°C for a period of 4 hours. Samples without post mold curing are designated by NPMC. 

Ea, above and below Tg. Three case studies illustrate the range of applicability of the bending beam setup and factors contributing to the stress state. The first is a comparison of two polymers for interlayer dielectrics PMDA-ODA (pyromellitic acid dianhydride - oxydiamine) and a bis-benzocyclobutene. The second is of a neat epoxy resin commonly used for microelectronics encapsulation (epoxidized ortho-cresol novolac cured with a phenolic novolac). The third is a screen-printable polyimide coating used for protection of the integrated-circuit chip. An outline of our stress model is sketched, and example results are presented. 

Resin I contains roughly equal amounts of diglycidyl ether of bisphenol A (DGEBA) and an epoxy cresol novolac. Sufficient dicyandiamide (DICY) as a curing agent is present such that the amine/epoxy ratio is 0.85. Monuron is present as an accelerator. The supplier s recommend standard cure is two hours at 127°C. Previous work (1 ) has shown that this cycle produces a fully cured system, as indicated by the disappearance of the epoxide absorbance band in the infrared spectrum. 

TYPICAL CLEAR CASTING DATA OF PHENOLIC-CURED XD-9053.00L COMPARED WITH EPOXY CRESOL NOVOLAC RESIN... 

Cure Kinetics of Epoxy Cresol Novolac Encapsulant for Microelectronics... 

The epoxy novolac resins are synthesized by reaction of phenolic or cresol novolacs with epichlorohydrin in the same fashion as the bisphenol A resins. The number of epoxy groups per molecule is dependent on the number of hydroxyls in the phenol novolac molecule and to the extent to which they are reacted. Complete epoxidation can be accomplished, but this will lead to steric factors, which could limit the useful size of the cured polymer. Thus, selective epoxidation is often practiced.9... 

Resin II contains tetraglycidyl methylene dianiline (TGMDA) as the principal epoxide with small amounts of a cresol novolac and DGEBA. DICY as curing agent is present in an amount such that the amine epoxy ratio is 0.25. Diuron is the accelerator. The supplier s recommended standard cure is the same as for SP250. However, in this system approximately 20 percent of the epoxide remains unreacted following the cure cycle (1 ). Selected resin plates were subjected to additional cure at 170°C and 220°C. The samples post cured at 220 C for forty minutes showed no residual epoxide absorbance in the IR spectrum. 

Expanded materials with excellent high-temperature properties are obtained when cresol novolacs are used as hardeners. A typical formulation is based on mixtures of bisphenol A resins and epoxy novolac resins which are cured by cresol novolacs and accelerated by suitable nitrogen-containing agents. 

Novolac epoxy resins, phenolic or cresol novolacs, are reacted with epichlorohydrin to produce these novolac epoxy resins which cure more rapidly than the epi-bis epoxies and have higher exotherms. These cured novolacs have higher heat-deflection temperatures than the epi-bis resins as shown in Table 2.8. The novolacs also have excellent resistance to solvents and chemicals when compared with that of an epi-bis resin as seen in Table 2.9. 

This class of compounds is one of the most important adhesive groups with applications ranging from consumer to aerospace markets. Epoxies are thermosets and are cross-linked during the cure cycle. The chemical stmcmre for a simple epoxy (ethylene oxide) in its unhardened state is shown in Figure 5.2. All epoxy compounds contain two or more of these groups. Epoxy resins form adducts with vinyl, acrylic, and polyester resins producing compounds such as phenol novolac, cresol novolac, bis-[4(2,3-epoxy propyoxy) phenyl] methane, and phenol hydrocarbon novalac [53]. 

These resins (Resole or Novolac) are used as curing agents or hardeners for epoxy molding compounds for electronics applications such as computer components. 0-cresol-formaldehyde resins have heen also used to modify phenol-formaldehyde resins, and in laminates. 

Ho et al (1996) examined polyol or polysiloxane thermoplastic polyurethanes (TPUs) as modifiers in cresol-formaldehye novolac epoxy resins cured with phenolic novolac resin for computer-chip encapsulation. A stable sea-island dispersion of TPU particles was achieved by the epoxy ring-opening with isocyanate groups of the urethane prepolymer to form an oxazolidone. The flexural modulus was reduced by addition of TPU and also the Tg was increased due to the rigid oxazolidone structure. Mayadunne et al (1999) extended this work to a series of phenol- and naphthol-based aralkyl epoxy resins. 

The primary resins used in this market are the radiation-curable epoxy acrylates, accounting for 60% of the resins used. A small amoimt of cycloaliphatic epoxies are also used in UV-curable inks and resists. Phenol and cresol epoxy no-volacs, and bisphenol A based epoxies are used in thermally cured formulations. The epoxy novolacs are used where higher heat resistance is needed such as in solder masks. Both free-radical and cationic-curable UV inks and colored base coats have grown rapidly because of the needs for higher line speeds, faster cleanup or line turnaround, less energy consumption, less capital for a new hne, and fewer emissions. 

Alcohol-soluble non-heat-reactive types are low MW novolacs derived from phenol or cresols that are used in the preparation of novolac epoxy resins, epoxy curing agents, epoxy-phenolic systems, and powder coatings. 

The increased functionality yields cured adhesives with higher crosslink densities resulting in higher temperature performance and increased chemical resistance. The functionality of commercially available, phenol based epoxy novolac resins varies from 2.3 to 6.0. Epoxy novolac resins can also be produced from substituted phenols like creosol and po-lyhydioxy phenols such as resorcinol. In the United States, Dow Chemical and Ciba-Geigy supply both phenol and cresol based epoxy novolac resins. 

---