Development of Photoacid and Photobase Generators as the Key Materials for Design of Novel Photopolymers

Novel photoacid and photobase generators for photopolymers developed in our laboratory are reviewed. Oxime sulfonates derived from 9-fluorenone and thioxanthone and imidosulfonates with thioxanthone skeleton or thianthrene moiety were developed as the i-line sensitive photoacid generators. Their photochemistry at i-line irradiation and their use in the photocrosslinking of polymers with pendant epoxy groups were investigated. The novel photosensitive polymers which are crosslinked photochemically in the presence of photoacid generators and the resulting crosslinked one can be degraded by the acids were developed. Carbamoyloximes, carbamates with imido structure, and quaternary ammonium salts were investigated as photobase generators. Copolymers with pendant carbamoyloxime moiety were proved to be very effectively crosslinked with photo-irradiation followed by baking, because amino and isocyanato groups, which were generated photochemically and thermochemically, respectively, promoted the formation of urea linkages. Thermal stability on latter two photobase generators is discussed. Copolymers with pendant acyloxime units in the block in both ends were found to be more effective crosslinkers for poly(glycidyl methacrylate) than those with random pendant groups. Novel photopolymers using photobase generators, which were photochemically crosslinked and followed by thermal degradation, were developed.

[1]  M. Shirai,et al.  Photo-Crosslinking of Poly(glycidyl methacrylate) Using Di-functional Photobase Generators , 2004 .

[2]  Masamitsu Shirai,et al.  Photo-cross-linkable polymers having degradable properties on heating , 2003 .

[4]  H. Yamato,et al.  Novel Photoacid Generators. , 2000 .

[5]  M. Shirai,et al.  Photoacid and Photobase Generators: Prospects and Their Use in the Development of Polymeric Photosensitive Systems. , 1998 .

[6]  Y. Tajima,et al.  Synthesis of Photocrosslinkable Polymers Having Pendant Oxetane Groups and Their Dissolution in Water by Thermolysis , 2005 .

[7]  J. Fouassier,et al.  Investigation of the photochemical properties of an important class of photobase generators: the O-acyloximes , 2002 .

[8]  D. Wicks,et al.  Blocked isocyanates III : Part A. Mechanisms and chemistry , 1999 .

[9]  Masamitsu Shirai,et al.  Photo-Cross-Linkable Polymers with Thermally Degradable Property , 2002 .

[10]  Masamitsu Shirai,et al.  Synthesis of i- and g-Line Sensitive Photoacid Generators and Their Application to Photopolymer Systems , 2003 .

[11]  Haruyuki Okamura,et al.  Evaluation of Quantum Yields for Decomposition of I-Line Sensitive Photoacid Generators , 2003 .

[12]  Masamitsu Shirai,et al.  Development of Novel Photosensitive Polymer Systems Using Photoacid and Photobase Generators , 2002 .

[13]  Haruyuki Okamura,et al.  Photocrosslinkable Polymers with Redissolution Property , 2002 .

[14]  Suyama Kanji,et al.  Thermally Stable Carbamates as Novel Photobase Generator , 2005 .

[15]  Haruyuki Okamura,et al.  Thermally crosslinkable–decrosslinkable system using diepoxy crosslinkers containing sulfonate ester moiety , 2004 .

[16]  D. Wicks,et al.  Blocked isocyanates III , 2001 .

[17]  Masamitsu Shirai,et al.  Synthesis of novel photo-cross-linkable polymers with redissolution property , 2004 .

[18]  J. Crivello,et al.  Development of Pyrene Photosensitizers for Cationic Photopolymerizations , 2002 .

[19]  Haruyuki Okamura,et al.  I-Line Sensitive Photoacid Generators and Their Use for Photocrosslinking of Polysilane/diepoxyfluorene Blend , 2003 .

[20]  M. Shirai,et al.  Photocrosslinking and Thermal Degradation of Epoxy-containing Polymers Using Photobase Generators , 2005 .

[21]  Haruyuki Okamura,et al.  I-Line Sensitive Photoacid and Photobase Generators and Their Use for Photocrosslinking System Based on Poly(vinylphenol) and Diepoxy Fluorene Derivatives. , 2002 .

[22]  M. Shirai,et al.  Photochemical formation of ammonium/thiolate complexes from quaternary ammonium thiocyanates and its use in crosslinking of polymers , 2006 .

[23]  J. Crivello,et al.  Anthracene electron-transfer photosensitizers for onium salt induced cationic photopolymerizations , 2003 .

[24]  Shogo Toda,et al.  Photocrosslinking system based on a poly(vinyl phenol)/thermally degradable diepoxy crosslinker blend , 2002 .

[25]  J. Cameron,et al.  Laser Flash Photolysis Study of Two Aromatic N-Oxyimidosulfonate Photoacid Generators , 2000 .