Photo-Initiated Formation of Amino Groups in Polymer Matrices and Its Applications to Functional Polymers

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The photo-initiated formation of amino groups in polymer matrices and its applications to functional polymers were investigated. Copolymers bearing pendent acyloxyimino(AOI) groups used in this study were O-acryloyl acetophenone oxime(AAPO) or O-methacryloyl acetophenone oxime(HAAPO) with styrene(St) or methyl methacrylate(MMA). An yield of formation of amino groups in the photolysis of a AAPO(26.3)-St copolymer film was 69.9% and double bonds were also formed in a 28.0% yield. The yield of amino groups did not depend on comonomers, irradiation wavelengths, and irradiation atmosphere but depended on the amount of AOI groups in copolymers i.e., the yield for a homopolymer of AAPO decreased to 25%. In the case of MAAPO(28.3)-St copolymer films, the yield of amino groups under nitrogen was 21.5% but a total amount of double bonds was 62.7%, which consisted of double bonds in main-chains and vinylidene-type double bonds. Under air, the yield of amino groups did not changed but the yield of … More donds bondrdecreased to 30.2% and at the same time main-chain scissions occurred. Applications of the AAPO copolymers to functional polymers were also investigated. The treatment of irradiated AAPO copolymer films with an aqueous HC1 solution rendered the copolymer surface hydrophilic and the films dyed well with an acid dye. Before irradiation, the copolymers dissolved in non-polar solvents such as benzene and toluene but the films treated with HC1 after irradiation dissolved in polar solvents such as ethanol and methanol. On the basis of these results, the applications of AAPO copolymers to dual-tone photoresists were investigated and it was proved that these copolymers have excellent properties as a positive-type photoresist. In the case of MAAPO copolymers, although the yield of amino group formation was lower compared with that of AAPO copolymers, efficient main-chain scissions were observed and the rate of the main-chain scissions was found to be accelerated by an increase in the content of AOI groups and irradiation time. This result was explained by a lowering of glass transition temperature of irradiated copolymers. Less