Effects of Curing Agents on the Adhesion of Epoxy Resin to Copper: A Density Functional Theory Study

Epoxy resins are widely used adhesives in industrial fields. To use epoxy resin as an adhesive, it is necessary to mix the epoxy resin with a hardener. Hardeners have various functional groups and skeletons, and the properties of epoxy resins vary depending on the hardener. Although the adhesion of epoxy resins has been extensively studied using density functional theory (DFT) calculations, few studies have evaluated the effect of hardener molecules. Therefore, in this study, DFT calculations of adhesion energies and bonding structures on Cu (111) and Cu₂O (111) surfaces are performed for model molecules of adducts of epoxy resin with hardeners having various functional groups and skeletons to evaluate the influence of the hardeners on the adhesion of epoxy resin to the metal surface. The adhesion energy to the Cu (111) surface is governed by the energy due to dispersion forces. Hardeners of the thiol type, which contain relatively heavy sulfur atoms, and hardeners with aromatic rings, displaying high planarity, enable the entire molecule to approach the metal surface, resulting in a relatively high adhesion strength. The calculations for the Cu₂O (111) surface show the adhesion strength is more strongly influenced by interactions such as hydrogen bonds between the surface and adhesive molecules than by dispersion forces. Therefore, in adhesion to Cu₂O (111), the benzylamine-epoxy adduct with hydrogen bonding and OH-π interactions with the surface, in addition to having a relatively flexible framework, shows a high adhesion strength.