O-Acyloximes are a class of photobase generators (PBGs) that release a primary amine upon irradiation. The generated amine can be used as a crosslinker for polymers bearing epoxy groups, providing a novel photo-induced crosslinking system. However, O-acyloximes also release a ketone by-product that migrates and exudes from the crosslinked polymer. To reduce the migration and elimination of the ketone, 4-vinylacetophenone O-phenylacetyloxime (PaVO) was proposed as a monomeric PBG, and its copolymer with glycidyl methacrylate (PaVO-co-GMA) was compared to poly(glycidyl methacrylate) (PGMA) containing acetophenone O-phenylacetyloxime (PaApO) as a molecular PBG (PaApO/PGMA). Film thickness, infrared (IR), and ultraviolet (UV) spectral changes upon irradiation clarified the vaporization of photoproducts from the PaApO/PGMA films, while such behavior was not observed for the PaVO-co-GMA films. Furthermore, when PaVO-co-GMA was blended with PGMA, less irradiation energy was required for its crosslinking when compared to that of PaApO/PGMA, which contained the same molar ratio of the O-acyloxime unit. (C) 2012 Elsevier Ltd. All rights reserved.