New epoxy/episulfide resin system for electronic and coating applications: Curing mechanisms and properties

This work involves research on a new resin system useful for printed circuit board and protective coating applications. The system provides excellent adhesion to copper and corrosion resistance for copper. The research involved detailed studies of the reaction mechanisms, and correlation of these mechanisms with the observed properties. ^ The epoxy/episulfide system, when used with a dicyandiamide (DICY) curing agent, exhibits better adhesion to copper substrate, a better pot life and prepreg storage life, a lower thermal expansion coefficient, a lower heat of reaction, a lower degradation temperature, and higher water absorption as compared with the standard epoxy system. ^ From model compound studies, the sulfur of the opened episulfide ring reacts with copper, resulting in a durable bond between the copper and matrix resin even after water boiling. Since the S- formed by the reaction of the episulfide with the curing agent easily reacts with both the episulfide and the epoxy, a C-S-C bond is formed and more unreacted curing agent remains as compared to the standard epoxy system. The new bond formation causes a lower thermal expansion coefficient and somewhat lower degradation temperature. The unreacted curing agent causes slightly higher water absorption. Since the episulfide ring has less stress than the epoxy ring the epoxy/episulfide system shows lower heat of reaction, i.e., a lower exotherm. and lower shrinkage. ^ The epoxy/episuffide system, when used with a polyamide curing agent, exhibits better corrosion protection for copper substrates, a lower thermal expansion coefficient and a lower degradation temperature. ^ From model compound studies, the curing reactions are changed by changing curing temperature and the presence of copper: the episulfide homopolymerization and the S--epoxy reactions increase in the case of room temperature curing or in the presence of copper. In the presence of copper, the sulfur of the episulfide also reacts with copper, although the amine of the curing agent is adsorbed on copper. The episulfide tends to move to the copper surface and polymerizes, resulting in a higher glass transition temperature near the interface than that of the bulk.