A water-developable flexographic printing plate consisting of poly(acrylonitrile-co-butadiene), polybutadiene, and carboxylated polyurethane as a polymer matrix, hexanediol dimethacrylate and polybutadiene diacrylate as reactive monomers, and benzildimethylketal as a photoinitiator was prepared and its photoreaction followed by structural change caused by the diffusion of unreacted monomers was characterized. Analysis combined C-13-NMR and attenuated total reflection (ATR) FTIR showed the photoreaction occurred predominantly at the surface of exposure to the light at first, and then the reaction proceeded to the direction of the opposite surface with an increase in the exposure time. Diffusion of unreacted monomers after the photoreaction from the unexposed side to the exposed side was monitored by ATR FTIR. The diffusivity of unreacted monomers was dependent on the extent of photoreaction in the plate and the molecular weight of diffusing monomers. (C) 2004 Wiley Periodicals, Inc.