DEVELOPMENTS OF PHOTORESPONSIBLE MATERIALS AND THEIR APPLICATIONS

感光材料的进展及其应用

• 批准号: 09554036
• 负责人: MIZUNO Kazuhiko
• 金额: $ 7.81万
• 依托单位: OSAKA PREFECTURE UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09554036/
• 关键词: Organosilicon Compound; Group 14 Organometallic Compound; Photoresponsible Polymer Compound; Photoresponsible Material; π,π-Interaction; Spirocompound; Aromatic Hydrocarbon; Patterning; 14族元素; π-π相互作用; ポリ(4-トリメチルシリルメチルスチレン); カルボキシル基生成; 光環化付加反応

Syntheses and photophysical and photochemical properties of trimethylsilyl-substituted aromatic hydrocarbons, spirocompounds having group 14 element as a spiroelement, and polystyrene derivatives having group 14 organometallic substituents have been examined for the purpose of the development of the photoresponsible materials and photoresponsible polymer compounds having group 14 elements and the following results were obtained. 1) The fluorescence quantum yields of trimethylsilyl-substituted aromatic hydrocarbons such as pyrene, anthracene, and phenanthrene were much higher than those of the corresponding unsubstituted aromatic hydrocarbons.2) 2,2'-Silaspirobiindan and its related compounds having group 14 elements were synthesized and characterized. The absorption and fluorescence spectra of the spirocompounds did not show any π,π-interaction between two aryl groups.3) KrF laser irradiation of thin film of poly (4-trimethylsilylmethylstyrene) under atmospheric condition induced oxygenation at the film surface and crosslinking inside the film. Since the crosslinking was an apparent two photon reaction and required the closely formed radicals, the efficiency of C-Si bond cleavage and the following radical formation at the 4-position of the benzene ring played the crucial role in the crosslinking ability.4) KrF laser irradiation of thin film of poly (4-trimethylstannylmethylstyrene) followed by heating at 500℃ under aerobic condition afforded the thin film pattern of SnOィイD22ィエD2.

为了开发具有第14族的光响应性材料和光响应性高分子化合物，对三甲基甲硅烷基取代的芳香族烃、具有第14族元素作为螺环元素的螺化合物以及具有第14族有机金属取代基的聚苯乙烯衍生物的合成以及光物理和光化学性质进行了研究1) 元素的荧光量子产率。芘、蒽、菲等三甲基硅基取代的芳香烃的荧光强度远高于相应的未取代的芳香烃。2)合成了2,2'-硅螺二茚满及其相关的14族元素化合物,并对其进行了吸收和荧光表征。螺环化合物的光谱没有显示两个芳基之间有任何 π,π 相互作用。3) KrF 激光聚(4-三甲基甲硅烷基甲基苯乙烯)薄膜在大气条件下的辐照引起薄膜表面的氧化和薄膜内部的交联，由于交联是明显的双光子反应并且需要紧密形成的自由基，因此C-Si键断裂的效率。苯环4位上的自由基形成对交联能力起着至关重要的作用。4）KrF激光照射聚薄膜(4-三甲基甲锡烷基甲基苯乙烯)，然后在有氧条件下加热至500℃，得到SnOD22D2的薄膜图案。

项目成果

Nobuyuki Ichinose: "Non-linear Laser Intensity Dependence of the Formation of Carboxylic Acid Groups at the Surface of Polymer Films : The Effect of Coupling of Radical Intermediates."Langmuir. 13. 2603-2605 (1997)

Nobuyuki Ichinose：“聚合物薄膜表面羧酸基团形成的非线性激光强度依赖性：自由基中间体偶联的影响。”Langmuir。

Akira Sugimoto: "Hydrobromic Acid-Dimethyl Sulfoxide Reagent for Dealkylation of 5,10-Dialkyl-5,10-dihydrophenazines : Synthesis of 10-Alkyl-2(10H)-phenazines."J.Heterocyclic Chem.. 36. 1057-1064 (1999)

Akira Sugimoto：“用于 5,10-二烷基-5,10-二氢吩嗪脱烷基化的氢溴酸-二甲基亚砜试剂：10-烷基-2(10H)-吩嗪的合成。”J.Heterocycl Chem.. 36. 1057-1064

Yasuharu Yoshimi: "A Novel Photorearrangement of Aryl Naphthylmethyl Ethers. Formation of Cyclohexa-2,4-dienone Derivatives"Tetrahedron Lett.. 39. 4683-4686 (1998)

Yasuharu Yoshimi：“芳基萘甲基醚的新颖光重排。环六-2,4-二烯酮衍生物的形成”Tetrahedron Lett.. 39. 4683-4686 (1998)

Akira Sugimoto: "Thermally Unstable 5-(9-Anthrylmethyl)-10-methyl-5,10-dihydrophenazine"J. Chem. Res.(S). 1999. 72-73 (1999)

Akira Sugimoto：“热不稳定的 5-(9-蒽甲基)-10-甲基-5,10-二氢吩嗪”J。

Toshiyuki Tamai: "Photochemical Oxygenation and Crosslinking of Poly(4-trimethylsilylmethyl-styrene) Thin Film by UV Irradiation"Macromolecules. 33(印刷中). (2000)

Toshiyuki Tamai：“通过紫外线照射进行聚（4-三甲基甲硅烷基甲基苯乙烯）薄膜的光化学氧化和交联”大分子（2000 年）。