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

研究了光引发聚合物基体中氨基的形成及其在功能聚合物中的应用。在这项研究中使用的带有侧链酰氧基亚氨基（AOI）基团的共聚物是O-丙烯酰基苯乙酮肟（AAPO）或O-甲基丙烯酰基苯乙酮肟（HAAPO）与苯乙烯（St）或甲基丙烯酸甲酯（MMA）。在AAPO（26.3）-St共聚物膜的光解中形成氨基的产率为69.9%，并且还以28.0%的产率形成双键。氨基的产率不取决于共聚单体、辐照波长和辐照气氛，而是取决于共聚物中AOI基团的量，即，AAPO均聚物的产率降低到25%。在MAAPO（28.3）-St共聚物膜的情况下，在氮气下氨基的产率为21.5%，但双键的总量为62.7%，其由主链中的双键和亚乙烯基型双键组成。在空气条件下，氨基的产率没有变化， ...更多信息 Donds键下降到30.2%，同时发生主链断裂。研究了AAPO共聚物在功能高分子中的应用。用HCl水溶液处理辐照的AAPO共聚物膜使得共聚物表面亲水，并且膜用酸性染料染色良好。在辐照之前，共聚物溶解在非极性溶剂如苯和甲苯中，但是在辐照之后用HCl处理的膜溶解在极性溶剂如乙醇和甲醇中。在此基础上，研究了AAPO共聚物在双色调光致抗蚀剂中的应用，证明了该共聚物作为正性光致抗蚀剂具有优异的性能。在MAAPO共聚物的情况下，虽然与AAPO共聚物相比，氨基形成的产率较低，但观察到有效的主链断裂，并且发现通过增加AOI基团的含量和照射时间来加速主链断裂的速率。这一结果被解释为辐照共聚物的玻璃化转变温度的降低。少

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