TWI771294B - Photosensitive composition and novel compound - Google Patents

Photosensitive composition and novel compound Download PDF

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TWI771294B
TWI771294B TW106110457A TW106110457A TWI771294B TW I771294 B TWI771294 B TW I771294B TW 106110457 A TW106110457 A TW 106110457A TW 106110457 A TW106110457 A TW 106110457A TW I771294 B TWI771294 B TW I771294B
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松井依純
岡田光裕
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日商艾迪科股份有限公司
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    • C07D251/34—Cyanuric or isocyanuric esters
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    • C08F2/00—Processes of polymerisation
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    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • G—PHYSICS
    • G02—OPTICS
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    • G02B5/20—Filters
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    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators

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  • Materials For Photolithography (AREA)
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  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

本發明係一種感光性組合物，其含有具有下述通式(1)所表示之取代基之化合物：

Figure 106110457-A0101-11-0001-1
(式中，R1 及R2 分別獨立地表示氫原子、鹵素原子、氰基、羥基、硝基、羧基、有具有取代基之情形之碳原子數1～40之烷基、碳原子數6～20之芳基、碳原子數7～20之芳基烷基、碳原子數2～20之含雜環之基、或三烷基矽烷基，j表示1～3之數，﹡意指於﹡部分與鄰接之基進行鍵結)。The present invention relates to a photosensitive composition containing a compound having a substituent represented by the following general formula (1):
Figure 106110457-A0101-11-0001-1
(in the formula, R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms in the case of having a substituent, and a carbon number of 6 Aryl of ~20, arylalkyl of 7 to 20 carbon atoms, heterocycle-containing group of 2 to 20 carbon atoms, or trialkylsilyl group, j represents the number of 1 to 3, and * means in * part is bonded to the adjacent base).

Description

感光性組合物及新穎化合物Photosensitive composition and novel compound

本發明係關於一種含有具有特定之結構，於常溫下為惰性，藉由加熱至特定溫度使之活化而表現出功能之化合物的感光性組合物、及新穎化合物。進而，本發明係關於一種於該感光性組合物中添加有著色劑之著色感光性組合物及使用該著色感光性組合物之彩色濾光片。The present invention relates to a photosensitive composition and a novel compound containing a compound having a specific structure, which is inert at normal temperature, and which is activated by heating to a specific temperature to exhibit a function. Furthermore, this invention relates to the coloring photosensitive composition which added the coloring agent to this photosensitive composition, and the color filter using this coloring photosensitive composition.

已知有為了提昇感光性組合物之耐候性或耐熱性，而添加紫外線吸收劑或抗氧化劑從而使其穩定化之方法(專利文獻1～4)。 酚系抗氧化劑及紫外線吸收劑具有捕獲對聚合物之劣化產生較大影響的自由基之作用，因此若將該等添加至聚合系內，則一般作為所謂聚合抑制劑發揮作用，引起硬化抑制之情況成為問題，因此業界開發出潛伏性添加劑(專利文獻5)。 但是，使用先前之潛伏性添加劑之組合物由於釋氣較多，故而存在污染加熱裝置、或組合物之物性降低之問題。存在裝置被污染、或物性降低之問題。又，使用先前之潛伏性添加劑之組合物由於硬化物之耐溶劑性較低，故而亦存在引起硬化物之溶出，例如使彩色濾光片之亮度降低之問題。 又，於專利文獻6中揭示有作為硬化劑有用之三烯丙基苯酚化合物，但並未提示含有該三烯丙基苯酚化合物之感光性組合物。 先前技術文獻 專利文獻 專利文獻1：日本專利特開2011-048382號公報 專利文獻2：美國專利申請案公開第2016/016919號說明書 專利文獻3：日本專利特開2015-108649號公報 專利文獻4：日本專利特開2015-132791號公報 專利文獻5：國際公開第2014/021023號 專利文獻6：日本專利特開平3-232832號公報In order to improve the weather resistance and heat resistance of a photosensitive composition, the method of adding an ultraviolet absorber or antioxidant, and making it stabilize is known (patent documents 1-4). Phenolic antioxidants and ultraviolet absorbers have the function of trapping free radicals that have a great influence on the deterioration of polymers. Therefore, when these are added to the polymerization system, they generally function as so-called polymerization inhibitors and cause hardening inhibition. Since the situation becomes a problem, a latent additive has been developed in the industry (Patent Document 5). However, the composition using the conventional latent additive has a problem of contamination of the heating device or deterioration of the physical properties of the composition due to a large amount of outgassing. There is a problem that the device is contaminated or its physical properties are degraded. In addition, the composition using the conventional latent additive has a problem of causing the dissolution of the hardened product, for example, reducing the brightness of the color filter, due to the low solvent resistance of the hardened product. Moreover, although the triallylphenol compound useful as a hardening|curing agent is disclosed in patent document 6, the photosensitive composition containing this triallylphenol compound is not suggested. Prior Art Document Patent Document Patent Document 1: Japanese Patent Laid-Open No. 2011-048382 Patent Document 2: US Patent Application Publication No. 2016/016919 Specification Patent Document 3: Japanese Patent Laid-Open No. 2015-108649 Patent Document 4: Japanese Patent Laid-Open No. 2015-132791 Patent Document 5: International Publication No. 2014/021023 Patent Document 6: Japanese Patent Laid-Open No. Hei 3-232832

因此，本發明之目的在於提供一種使用於常溫下為惰性，藉由加熱至特定溫度使之活化而表現出作為抗氧化劑或紫外線吸收劑之功能的化合物之釋氣較少且硬化物之耐溶劑性較高之感光性組合物。又，本發明之另一目的在於提供一種於上述感光性組合物中添加有著色劑之著色感光性組合物、尤其適於彩色濾光片之著色感光性組合物。 本發明者等反覆努力研究，結果發現，使用具有特定之保護基之化合物之感光性組合物之釋氣較少，其硬化物之耐溶劑性較高，又，發現於上述感光性組合物中添加有著色劑之著色感光性組合物不會使光學濾光片(尤其彩色濾光片)之亮度降低，適於液晶顯示面板等圖像顯示裝置用彩色濾光片，從而達成本發明。 本發明係基於上述見解而完成者，提供一種含有具有下述通式(1)所表示之取代基之化合物之感光性組合物。 [化1]

Figure 02_image005
(式中，R1 及R2 分別獨立地表示氫原子、鹵素原子、氰基、羥基、硝基、羧基、有具有取代基之情形之碳原子數1～40之烷基、有具有取代基之情形之碳原子數6～20之芳基、有具有取代基之情形之碳原子數7～20之芳基烷基、有具有取代基之情形之碳原子數2～20之含雜環之基或三烷基矽烷基， R1 及R2 所表示之烷基或芳基烷基中之亞甲基有被取代為於氧原子不相鄰之條件下將選自-O-、-S-、-CO-、-O-CO-、-CO-O-、-O-CO-O-、-S-CO-、-CO-S-、-S-CO-O-、-O-CO-S-、-CO-NH-、-NH-CO-、-NH-CO-O-、-NR'-、-S-S-或-SO2 -中之基組合而成之基之情形，R'表示氫原子或碳原子數1～8之烷基， j表示1～3之數， ﹡意指於﹡部分與鄰接之基進行鍵結)Therefore, an object of the present invention is to provide a compound which is inert at normal temperature, activated by heating to a specific temperature, and exhibits a function as an antioxidant or an ultraviolet absorber, which has less outgassing and a hardened product that is resistant to solvents. High-performance photosensitive composition. Moreover, another object of this invention is to provide the coloring photosensitive composition which added the coloring agent to the said photosensitive composition, especially the coloring photosensitive composition suitable for a color filter. The inventors of the present invention have repeatedly researched and found that the photosensitive composition using the compound having a specific protecting group has less outgassing and higher solvent resistance of the cured product. Furthermore, it was found in the above-mentioned photosensitive composition. The coloring photosensitive composition to which the colorant is added does not reduce the brightness of optical filters (especially color filters), and is suitable for color filters for image display devices such as liquid crystal display panels, thereby achieving the present invention. The present invention was completed based on the above findings, and provides a photosensitive composition containing a compound having a substituent represented by the following general formula (1). [hua 1]
Figure 02_image005
(in the formula, R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms in the case of having a substituent, a group having a substituent In the case of an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms in the case of having a substituent, and a heterocyclic ring-containing group having 2 to 20 carbon atoms in the case of having a substituent group or trialkylsilyl group, the methylene group in the alkyl group or arylalkyl group represented by R 1 and R 2 has been substituted to be selected from -O-, -S under the condition that the oxygen atoms are not adjacent -, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO -S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-, -SS- or -SO 2 - in the case of a combination of radicals, R' Represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, j represents a number of 1 to 3, ﹡ means that the ﹡ part is bonded to an adjacent group)

以下，基於較佳之實施形態對本發明進行詳細說明。 本發明之感光性組合物含有具有上述通式(I)所表示之取代基之化合物。 於具有上述通式(I)所表示之取代基之化合物中，下述通式(I-A)所表示者尤其耐熱性較高且釋氣較少，故而較佳。 [化2]

Figure 02_image007
(式中，n表示1～10之整數， X1 表示n價鍵結基， R1 、R2 及j與上述通式(I)相同) 作為R1 及R2 所表示之鹵素原子，可列舉氟、氯、溴、碘， 作為R1 及R2 所表示之碳原子數1～20之烷基，可列舉：甲基、乙基、丙基、異丙基、丁基、第二丁基、第三丁基、異丁基、戊基、異戊基、第三戊基、環戊基、己基、2-己基、3-己基、環己基、4-甲基環己基、庚基、2-庚基、3-庚基、異庚基、第三庚基、1-辛基、異辛基、第三辛基、金剛烷基等， 作為R1 及R2 所表示之碳原子數6～20之芳基，可列舉：苯基、萘基、蒽基、菲基、茀基、茚基、2-甲基苯基、3-甲基苯基、4-甲基苯基、4-乙烯基苯基、3-異丙基苯基、4-異丙基苯基、4-丁基苯基、4-異丁基苯基、4-第三丁基苯基、4-己基苯基、4-環己基苯基、4-辛基苯基、4-(2-乙基己基)苯基、4-硬脂基苯基、2,3-二甲基苯基、2,4-二甲基苯基、2,5-二甲基苯基、2,6-二甲基苯基、3,4-二甲基苯基、3,5-二甲基苯基、2,4-二第三丁基苯基、2,5-二第三丁基苯基、2,6-二第三丁基苯基、2,4-二第三戊基苯基、2,5-二第三戊基苯基、2,5-二第三辛基苯基、2,4-二異丙苯基苯基、4-環己基苯基、(1,1'-聯苯)-4-基、2,4,5-三甲基苯基、二茂鐵基等， 作為R1 及R2 所表示之碳原子數7～20之芳基烷基，可列舉：苄基、1-甲基-1-苯基乙基、1-萘基甲基、9-蒽基甲基、9-茀基、3-苯基丙基、甲基-2-苯基丙烷-2-基、二苯基甲基、三苯基甲基、苯乙基、苯乙烯基、桂醯基等， 作為R1 及R2 所表示之碳原子數2～20之含雜環之基，可列舉：將吡啶環、嘧啶環、嗒𠯤環、哌啶環、吡喃環、吡唑啉環、三𠯤環、吡咯啉環、喹啉環、異喹啉環、咪唑啉環、苯并咪唑啉環、三唑啉環、呋喃環、苯并呋喃環、噻二唑啉環、噻唑啉環、苯并噻唑啉環、噻吩環、㗁唑啉環、苯并㗁唑啉環、異噻唑啉環、異㗁唑啉環、吲哚環、吡咯啶環、哌啶酮環、二㗁烷環等雜環與亞甲基鏈組合而成之基， 作為R1 及R2 所表示之三烷基矽烷基，可列舉：三甲基矽烷、三乙基矽烷、乙基二甲基矽烷等經碳原子數1～6之烷基(3個烷基相同或不同)取代之矽烷基。 作為R'所表示之碳原子數1～8之烷基，可列舉R1 所表示之上述烷基中之滿足特定之碳原子數者。 作為取代R1 及R2 所表示之碳原子數1～40之烷基、碳原子數6～20之芳基、碳原子數7～20之芳基烷基或碳原子數2～20之含雜環之基之取代基，可列舉：乙烯基、烯丙基、丙烯酸基、甲基丙烯酸基等乙烯性不飽和基；氟、氯、溴、碘等鹵素原子；乙醯基、2-氯乙醯基、丙醯基、辛醯基、丙烯醯基、甲基丙烯醯基、苯基羰基(苯甲醯基)、酞醯基、4-三氟甲基苯甲醯基、特戊醯基、鄰羥苯甲醯基、草醯基、硬脂醯基、甲氧基羰基、乙氧基羰基、第三丁氧基羰基、正十八烷氧基羰基、胺甲醯基等醯基；乙醯氧基、苯甲醯氧基等醯氧基；胺基、乙基胺基、二甲基胺基、二乙基胺基、丁基胺基、環戊基胺基、2-乙基己基胺基、十二烷基胺基、苯胺基、氯苯基胺基、甲苯胺基、甲氧苯胺基、N-甲基-苯胺基、二苯基胺基、萘基胺基、2-吡啶基胺基、甲氧基羰基胺基、苯氧基羰基胺基、乙醯基胺基、苯甲醯基胺基、甲醯基胺基、特戊醯基胺基、月桂醯基胺基、胺甲醯基胺基、N,N-二甲基胺基羰基胺基、N,N-二乙基胺基羰基胺基、嗎啉基羰基胺基、甲氧基羰基胺基、乙氧基羰基胺基、第三丁氧基羰基胺基、正十八烷氧基羰基胺基、N-甲基-甲氧基羰基胺基、苯氧基羰基胺基、胺磺醯基胺基、N,N-二甲基胺基磺醯基胺基、甲基磺醯基胺基、丁基磺醯基胺基、苯基磺醯基胺基等取代胺基；磺醯胺基、磺醯基、羧基、氰基、磺基、羥基、硝基、巰基、醯亞胺基、胺甲醯基、磺醯胺基、膦酸基、磷酸基或羧基、磺基、膦酸基、磷酸基之鹽等。 作為R1 及R2 ，氫原子、碳原子數1～8之烷基、碳原子數6～12之芳基由於釋氣較少，故而較佳。R1 及R2 為氫原子或具有支鏈之碳原子數1～8之烷基、尤其第三丁基中之任一者時，釋氣較少，故而更佳。 於上述通式(I-A)中，X1 表示n價之鍵結基，具體而言，例如表示直接鍵、氫原子、氮原子、氧原子、硫原子、磷原子、下述(I-a)或(I-b)所表示之基、-CO-、-NH-CO-、-CO-NH-、-NR3- 、-OR3 、-SR3 、-NR3 R4 、或具有與n相同之價數之有具有取代基之情形之碳原子數1～120之脂肪族烴基、有具有取代基之情形之碳原子數6～35之含芳香環烴基、或有具有取代基之情形之碳原子數2～35之含雜環之基，R3 及R4 表示氫原子、有具有取代基之情形之碳原子數1～35之脂肪族烴基、有具有取代基之情形之碳原子數6～35之含芳香環烴基或有具有取代基之情形之碳原子數2～35之含雜環之基，脂肪族烴基、含芳香環烴基及含雜環之基有被取代為選自碳-碳雙鍵、-O-、-S-、-CO-、-O-CO-、-CO-O-、-O-CO-O-、-S-CO-、-CO-S-、-S-CO-O-、-O-CO-S-、-CO-NH-、-NH-CO-、-NH-CO-O-、-O-CO-NH-、-NR'-、-S-S-、-SO2 -或氮原子中之基之情形。 其中，於X1 為氮原子、磷原子或下述(I-a)或(I-b)所表示之鍵結基之情形時，n為3，於X1 為氧原子或硫原子、-CO-、-NH-CO-、-CO-NH-或-NR3- 之情形時，n為2，於X1 為氫原子、-OR3 、-SR3 或-NR3 R4 之情形時，n為1，X1 有與苯環成為一體而形成環之情形。 [化3]
Figure 02_image009
(﹡意指於﹡部分與鄰接之基進行鍵結) 上述通式(I-A)所表示之化合物具有於X1 所表示之n價鍵結基鍵結有n個特定基之結構。該n個基相互相同或不同。n之值為1～10，就低釋氣之觀點而言，較佳為2～6。 作為上述通式(I-A)中之由X1 表示，具有與n相同之價數之有具有取代基之情形之碳原子數1～120之脂肪族烴基，作為n為一價者，例如可列舉：甲基、乙基、丙基、異丙基、環丙基、丁基、第二丁基、第三丁基、異丁基、戊基、異戊基、第三戊基、環戊基、己基、2-己基、3-己基、環己基、雙環己基、1-甲基環己基、庚基、2-庚基、3-庚基、異庚基、第三庚基、正辛基、異辛基、第三辛基、2-乙基己基、壬基、異壬基、癸基等烷基；甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、第二丁氧基、第三丁氧基、異丁氧基、戊氧基、異戊氧基、第三戊氧基、己氧基、環己氧基、庚氧基、異庚氧基、第三庚氧基、正辛氧基、異辛氧基、第三辛氧基、2-乙基己氧基、壬氧基、癸氧基等烷氧基；甲硫基、乙硫基、丙硫基、異丙硫基、丁硫基、第二丁硫基、第三丁硫基、異丁硫基、戊硫基、異戊硫基、第三戊硫基、己硫基、環己硫基、庚硫基、異庚硫基、第三庚硫基、正辛硫基、異辛硫基、第三辛硫基、2-乙基己硫基等烷硫基；乙烯基、1-甲基乙烯基、2-甲基乙烯基、2-丙烯基、1-甲基-3-丙烯基、3-丁烯基、1-甲基-3-丁烯基、異丁烯基、3-戊烯基、4-己烯基、環己烯基、雙環己烯基、庚烯基、辛烯基、癸烯基、十五烯基、二十烯基、二十三烯基等烯基；及該等基經後述之取代基取代之基等； 作為n為二價者，可列舉：亞甲基、伸乙基、伸丙基、伸丁基、丁基二基等伸烷基；上述伸烷基之亞甲基鏈被取代為-O-、-S-、-CO-O-、-O-CO-者；乙二醇、丙二醇、丁二醇、戊二醇、己二醇等二醇之殘基；乙二硫醇、丙二硫醇、丁二硫醇、戊二硫醇、己二硫醇等二硫醇之殘基；及該等基經後述之取代基取代之基等； 作為n為三價者，例如可列舉：次丙基、1,1,3-次丁基等次烷基；及該等基經後述之取代基取代之基。 作為具有與n相同之價數之有具有取代基之情形之碳原子數6～35之含芳香環烴基，作為n為一價者，可列舉：苄基、苯乙基、二苯基甲基、三苯基甲基、苯乙烯基、桂醯基等芳基烷基；苯基、萘基等芳基；苯氧基、萘氧基等芳基氧基；苯硫基、萘硫基等芳基硫基；及該等基經後述之取代基取代之基等； 作為n為二價者，可列舉：伸苯基、伸萘基等伸芳基；鄰苯二酚、雙酚等二官能苯酚之殘基；2,4,8,10-四氧雜螺[5,5]十一烷等；及該等基經後述之取代基取代之基； 作為n為三價者，可列舉：苯基-1,3,5-三亞甲基及該等基經後述之取代基取代之基。 作為具有與n相同之價數之有具有取代基之情形之碳原子數2～35之含雜環之基，作為n為一價者，可列舉：吡啶基、嘧啶基、嗒𠯤基、哌啶基、吡喃基、吡唑基、三𠯤基、吡咯基、喹啉基、異喹啉基、咪唑基、苯并咪唑基、三唑基、呋喃基(furyl)、呋喃基(furanyl)、苯并呋喃基、噻吩基、苯硫基、苯并苯硫基、噻二唑基、噻唑基、苯并噻唑基、㗁唑基、苯并㗁唑基、異噻唑基、異㗁唑基、吲哚基、2-吡咯啶酮-1-基、2-哌啶酮-1-基、2,4-二氧基咪唑啶-3-基、2,4-二氧基㗁唑啶-3-基、苯并三唑基等；及該等基經後述之取代基取代之基等； 作為n為二價者，可列舉：具有吡啶環、嘧啶環、哌啶環、哌𠯤環、三𠯤環、呋喃環、噻吩環、吲哚環等之基；及該等基經後述之取代基取代之基； 作為n為三價者，可列舉：具有異三聚氰酸環之基、具有三𠯤環之基；及該等基經後述之取代基取代之基。 作為R3 及R4 所表示之有具有取代基之情形之碳原子數1～35之脂肪族烴基，可列舉上述X1 所表示之脂肪族烴基及該脂肪族烴基與上述取代基之組合中滿足特定之碳原子數者， 作為R3 及R4 所表示之有具有取代基之情形之碳原子數6～35之含芳香環烴基及有具有取代基之情形之碳原子數2～35之含雜環之基，可列舉：上述X1 所表示之碳原子數6～35之含芳香環烴基及碳原子數2～35之含雜環之基以及將該等基與後述之取代基組合而成之基中滿足特定之碳原子數者。 作為取代基，可列舉：乙烯基、烯丙基、丙烯酸基、甲基丙烯酸基等乙烯性不飽和基；氟、氯、溴、碘等鹵素原子；乙醯基、2-氯乙醯基、丙醯基、辛醯基、丙烯醯基、甲基丙烯醯基、苯基羰基(苯甲醯基)、酞醯基、4-三氟甲基苯甲醯基、特戊醯基、鄰羥苯甲醯基、草醯基、硬脂醯基、甲氧基羰基、乙氧基羰基、第三丁氧基羰基、正十八烷氧基羰基、胺甲醯基等醯基；乙醯氧基、苯甲醯氧基等醯氧基；胺基、乙基胺基、二甲基胺基、二乙基胺基、丁基胺基、環戊基胺基、2-乙基己基胺基、十二烷基胺基、苯胺基、氯苯基胺基、甲苯胺基、甲氧苯胺基、N-甲基-苯胺基、二苯基胺基、萘基胺基、2-吡啶基胺基、甲氧基羰基胺基、苯氧基羰基胺基、乙醯基胺基、苯甲醯基胺基、甲醯基胺基、特戊醯基胺基、月桂醯基胺基、胺甲醯基胺基、N,N-二甲基胺基羰基胺基、N,N-二乙基胺基羰基胺基、嗎啉基羰基胺基、甲氧基羰基胺基、乙氧基羰基胺基、第三丁氧基羰基胺基、正十八烷氧基羰基胺基、N-甲基-甲氧基羰基胺基、苯氧基羰基胺基、胺磺醯基胺基、N,N-二甲基胺基磺醯基胺基、甲基磺醯基胺基、丁基磺醯基胺基、苯基磺醯基胺基等取代胺基；磺醯胺基、磺醯基、羧基、氰基、磺基、羥基、硝基、巰基、醯亞胺基、胺甲醯基、磺醯胺基、膦酸基、磷酸基或羧基、磺基、膦酸基、磷酸基之鹽等，該等基有進而被取代之情形。又，羧基及磺基有形成鹽之情形。 於上述通式(I-A)中，n為2～6時，X1 亦可分別如下述通式 (1)～(5)般表示。 [化4]
Figure 02_image011
(上述通式(1)中，Y1 表示單鍵、-CR5 R6- 、-NR7- 、二價之碳原子數1～35之脂肪族烴基、碳原子數6～35之芳香族烴基或碳原子數2～35之含雜環之基、或下述(1-1)～(1-3)所表示之任一取代基， 該脂肪族烴基有被取代為-O-、-S-、-CO-、-COO-、-OCO-、-NH-、-SO2 -、-CONH-或-NHCO-、或以氧原子不相鄰之方式將該等組合而成之鍵結基之情形， Z1 及Z2 分別獨立地表示直接鍵、-O-、-S-、＞CO、-CO-O-、-O-CO-、-SO2 -、-SS-、-SO-、-NR7- 或-PR7- ， R5 、R6 及R7 分別獨立地表示氫原子、有具有取代基之情形之碳原子數1～35之脂肪族烴基、有具有取代基之情形之碳原子數6～35之芳香族烴基或有具有取代基之情形之碳原子數2～35之含雜環之基， ﹡意指於﹡部分與鄰接之基進行鍵結) [化5]
Figure 02_image013
(上述式中，R8 表示氫原子、或者有具有取代基之情形之苯基或碳原子數3～10之環烷基， R9 表示碳原子數1～10之烷基、碳原子數1～10之烷氧基、碳原子數2～10之烯基或鹵素原子，上述烷基、烷氧基及烯基有具有取代基之情形， f為0～5之整數， ﹡意指於﹡部分與鄰接之基進行鍵結) [化6]
Figure 02_image015
(﹡意指於﹡部分與鄰接之基進行鍵結) [化7]
Figure 02_image017
(上述式中，R10 及R11 分別獨立地表示有具有取代基之情形之碳原子數1～10之烷基、有具有取代基之情形之碳原子數6～20之芳基、有具有取代基之情形之碳原子數6～20之芳基氧基、有具有取代基之情形之碳原子數6～20之芳基硫基、有具有取代基之情形之碳原子數6～20之芳基烯基、有具有取代基之情形之碳原子數7～20之芳基烷基、有具有取代基之情形之碳原子數2～20之含雜環之基或鹵素原子， 該烷基及芳基烷基中之亞甲基有被取代為不飽和鍵、-O-或-S-之情形， R10 有由鄰接之R10 彼此形成環之情形， p表示0～4之數， q表示0～8之數， g表示0～4之數， h表示0～4之數， g與h之數量之合計為2～4， ﹡意指於﹡部分與鄰接之基進行鍵結) [化8]
Figure 02_image019
(上述通式(2)中，Y11 表示三價之碳原子數3～35之脂肪族烴基、碳原子數3～35之脂環族烴基、碳原子數6～35之芳香族烴基或碳原子數2～35之含雜環之基， Z1 、Z2 及Z3 分別獨立地表示直接鍵、-O-、-S-、-CO-、-CO-O-、-O-CO-、-SO2 -、-SS-、-SO-、-NR12 -或-PR12 -， R12 表示氫原子、有具有取代基之情形之碳原子數1～35之脂肪族烴基、有具有取代基之情形之碳原子數6～35之芳香族烴基或有具有取代基之情形之碳原子數2～35之含雜環之基， 脂肪族烴基有被取代為碳-碳雙鍵、-O-、-S-、-CO-、-COO-、-OCO-、-NH-、-SO2 -、-CONH-或-NHCO-、或以氧原子不相鄰之方式將該等組合而成之鍵結基之情形， ﹡意指於﹡部分與鄰接之基進行鍵結) [化9]
Figure 02_image021
(上述通式(3)中，Y12 表示碳原子、或四價之碳原子數1～35之脂肪族烴基、碳原子數6～35之芳香族烴基或碳原子數2～35之含雜環之基， 該脂肪族烴基有被取代為碳-碳雙鍵、-O-、-S-、-CO-、-COO-、-OCO-、-NH-、-SO2 -、-CONH-或-NHCO-、或以氧原子不相鄰之方式將該等組合而成之鍵結基之情形， Z1 ～Z4 分別獨立為與上述通式(2)中之Z1 ～Z3 所表示之基相同之範圍之基， ﹡意指於﹡部分與鄰接之基進行鍵結) [化10]
Figure 02_image023
(上述通式(4)中，Y13 表示五價之碳原子數2～35之脂肪族烴基、碳原子數6～20之芳香族烴基或碳原子數2～20之含雜環之基， 該脂肪族烴基有被取代為碳-碳雙鍵、-O-、-S-、-CO-、-COO-、-OCO-、-NH-、-SO2 -、-CONH-或-NHCO-、或以氧原子不相鄰之方式將該等組合而成之鍵結基之情形， Z1 ～Z5 分別獨立為與上述通式(2)中之Z1 ～Z3 所表示之基相同之範圍之基， ﹡意指於﹡部分與鄰接之基進行鍵結) [化11]
Figure 02_image025
(上述通式(5)中，Y14 表示六價之碳原子數2～35之脂肪族烴基、碳原子數6～35之芳香族烴基或碳原子數2～35之含雜環之基， 該脂肪族烴基有被取代為碳-碳雙鍵、-O-、-S-、-CO-、-COO-、-OCO-、-NH-、-SO2 -、-CONH-或-NHCO-、或以氧原子不相鄰之方式將該等組合而成之鍵結基之情形， Z1 ～Z6 分別獨立為與上述通式(2)中之Z1 ～Z3 所表示之基相同之範圍之基， ﹡意指於﹡部分與鄰接之基進行鍵結) 於上述通式(1)中，作為R5 、R6 及R7 所表示之有具有取代基之情形之碳原子數1～35之脂肪族烴基，可列舉：作為上述通式(I-A)中之X1 所表示之n價鍵結基而例示之一價脂肪族烴基、及該等基經作為表示上述通式(I-A)中之X1 所表示之n價鍵結基的基之取代基而例示者取代之基中滿足特定之碳原子數者等， 作為R5 、R6 及R7 所表示之有具有取代基之情形之碳原子數6～35之含芳香環烴基，可列舉：作為上述通式(I-A)中之X1 所表示之n價鍵結基而例示之一價含芳香環烴基、及該等基經作為表示上述通式(I-A)中之X1 所表示之n價鍵結基的基之取代基而例示者取代之基中滿足特定之碳原子數者等， 作為R5 、R6 及R7 所表示之有具有取代基之情形之碳原子數2～35之含雜環之基，可列舉：作為上述通式(I-A)中之X1 所表示之n價鍵結基而例示之一價之含雜環之基、及該等基經作為表示上述通式(I-A)中之X1 所表示之n價鍵結的基之取代基而例示者取代之基中滿足特定之碳原子數者等。 又，於上述通式(1)中，作為Y1 所表示之二價之碳原子數1～35之脂肪族烴基，可列舉：作為上述通式(I-A)中之X1 所表示之n價鍵結基而例示之二價之脂肪族烴基、及該等基經作為表示上述通式(I-A)中之X1 所表示之n價鍵結基的基之取代基而例示者取代之基中滿足特定之碳原子數者等， 作為Y1 所表示之二價之碳原子數6～35之含芳香環烴基，可列舉：作為上述通式(I-A)中之X1 所表示之n價鍵結基而例示之二價之含芳香環烴基、及該等基經作為表示上述通式(I-A)中之X1 所表示之n價鍵結基的基之取代基而例示者取代之基中滿足特定之碳原子數者等， 作為Y1 所表示之二價之碳原子數2～35之含雜環之基，可列舉：作為上述通式(I-A)中之X1 所表示之n價鍵結基而例示之二價之含芳香環烴基、及該等基經作為表示上述通式(I-A)中之X1 所表示之n價鍵結基的基之取代基而例示者取代之基中滿足特定之碳原子數者等。 於上述(1-1)所表示之取代基中，作為R8 所表示之碳原子數3～10之環烷基，可列舉：環丙基、環丁基、環戊基、環庚基、環辛基等， 作為R9 所表示之碳原子數1～10之烷基，可列舉作為R1 及R2 所表示之碳原子數1～40之烷基而例示之基中滿足特定之碳原子數之基等， 作為R9 所表示之碳原子數1～10之烷氧基，可列舉：甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、第二丁氧基、第三丁氧基、異丁氧基、戊氧基、異戊氧基、第三戊氧基、己氧基、環己氧基、庚氧基、異庚氧基、第三庚氧基、正辛氧基、異辛氧基、第三辛氧基、2-乙基己氧基、壬氧基、癸氧基等， 苯基、環烷基、烷基、烷氧基及烯基之取代基與作為上述通式(I-A)中之X1 所表示之n價鍵結基之取代基而例示者相同。 於上述(1-3)所表示之基中，作為R10 及R11 所表示之有具有取代基之情形之碳原子數1～10之烷基，可列舉作為R1 及R2 所表示之碳原子數1～40之烷基而例示之基中滿足特定之碳原子數之基等， 作為R10 及R11 所表示之有具有取代基之情形之碳原子數6～20之芳基，可列舉：作為R1 及R2 所表示之碳原子數6～20之芳基而例示之基等， 作為R10 及R11 所表示之有具有取代基之情形之碳原子數6～20之芳基氧基，可列舉：苯氧基、萘氧基、2-甲基苯氧基、3-甲基苯氧基、4-甲基苯氧基、4-乙烯基苯氧基、3-異丙基苯氧基、4-異丙基苯氧基、4-丁基苯氧基、4-第三丁基苯氧基、4-己基苯氧基、4-環己基苯氧基、4-辛基苯氧基、4-(2-乙基己基)苯氧基、2,3-二甲基苯氧基、2,4-二甲基苯氧基、2,5-二甲基苯氧基、2,6-二甲基苯氧基、3,4-二甲基苯氧基、3,5-二甲基苯氧基、2,4-二第三丁基苯氧基、2,5-二第三丁基苯氧基、2,6-二第三丁基苯氧基、2,4-二第三戊基苯氧基、2,5-第三戊基苯氧基、4-環己基苯氧基、2,4,5-三甲基苯氧基、二茂鐵氧基等基， 作為R10 及R11 所表示之有具有取代基之情形之碳原子數6～20之芳基硫基，可列舉：將上述有具有取代基之情形之碳原子數6～20之芳基氧基之氧原子取代為硫原子之基等， 作為R10 及R11 所表示之有具有取代基之情形之碳原子數8～20之芳基烯基，可列舉：將上述有具有取代基之情形之碳原子數6～20之芳基氧基之氧原子取代為乙烯基、烯丙基、1-丙烯基、異丙烯基、2-丁烯基、1,3-丁二烯基、2-戊烯基、2-辛烯基等烯基之基等， 作為R10 及R11 所表示之有具有取代基之情形之碳原子數7～20之芳基烷基，可列舉：作為R1 及R2 所表示之碳原子數7～20之芳基烷基而例示之基等， 作為R10 及R11 所表示之有具有取代基之情形之碳原子數2～20之含雜環之基，可列舉：作為R1 及R2 所表示之碳原子數2～20之含雜環之基而例示之基等。 作為上述通式(2)中之Y11 所表示之三價之碳原子數1～35之脂肪族烴基，可列舉：作為上述通式(I-A)中之X1 所表示之n價鍵結基而例示之三價脂肪族烴基及該等基經作為上述通式(I-A)中之X1 所表示之n價鍵結基之取代基而例示者取代之基中滿足特定之碳原子數者等經Z1 、Z2 及Z3 取代之三價基等， 作為上述通式(2)中之Y11 所表示之三價之碳原子數3～35之脂環族烴基，可列舉：由環戊基、環己基、環庚基、環辛基、環癸基、1-金剛烷基、2-金剛烷基、降金剛烷基、2-甲基金剛烷基、降𦯉基、異降𦯉基、全氫萘基、全氫蒽基、雙環[1.1.0]丁基、雙環[1.1.1]戊基、雙環[2.1.0]戊基、雙環[3.1.0]己基、雙環[2.1.1]己基、雙環[2.2.0]己基、雙環[4.1.0]庚基、雙環[3.2.0]庚基、雙環[3.1.1]庚基、雙環[2.2.1]庚基、雙環[5.1.0]辛基、雙環[4.2.0]辛基、雙環[4.1.1]辛基、雙環[3.3.0]辛基、雙環[3.2.1]辛基、雙環[2.2.2]辛基、螺[4,4]壬基、螺[4,5]癸基、十氫萘、三環癸基、四環十二烷基、雪松醇基、環十二烷基等基所衍生之三價基等， 作為Y11 所表示之三價之碳原子數6～35之含芳香環烴基，可列舉：作為上述通式(I-A)中之X1 所表示之n價鍵結基而例示之三價之含芳香環烴基及該等基經作為上述通式(I-A)中之X1 所表示之n價鍵結基之取代基而例示者取代之基中滿足特定之碳原子數者等， 作為Y11 所表示之三價之碳原子數2～35之含雜環之基，可列舉：作為上述通式(I-A)中之X1 所表示之n價鍵結基而例示之三價含雜環之基及該等基經作為上述通式(I-A)中之X1 所表示之n價鍵結基之取代基而例示者取代之基中滿足特定之碳原子數者等。 又，作為R12 所表示之有具有取代基之情形之碳原子數1～35之脂肪族烴基、有具有取代基之情形之碳原子數6～35之芳香族烴基及有具有取代基之情形之碳原子數2～35之含雜環之基，分別可列舉上述通式(1)中之R5 、R6 及R7 之說明中所例示之脂肪族烴基、含芳香環烴基、含雜環之基。 於上述通式(3)中，作為Y12 所表示之四價之碳原子數1～35之脂肪族烴基，可列舉：由作為上述通式(I-A)中之X1 所表示之n價鍵結基而例示之一價～三價之脂肪族烴基及該等基經作為上述通式(I-A)中之X1 所表示之n價鍵結基之取代基而例示者取代之基所衍生之四價基中滿足特定之碳原子數者等， 作為Y12 所表示之四價之碳原子數6～35之含芳香環烴基，可列舉：由作為上述通式(I-A)中之X1 所表示之n價鍵結基而例示之一價～三價之含芳香環烴基及該等基經作為上述通式(I-A)中之X1 所表示之n價鍵結基之取代基而例示者取代之基所衍生之四價之基中滿足特定之碳原子數者等， 作為Y12 所表示之四價之碳原子數2～35之含雜環之基，可列舉：由作為上述通式(I-A)中之X1 所表示之n價鍵結基而例示之一價～三價之含雜環之基及該等基經作為上述通式(I-A)中之X1 所表示之n價鍵結基之取代基而例示者取代之基所衍生之四價基中滿足特定之碳原子數者等。 作為上述通式(4)中之Y13 所表示之五價之碳原子數2～35之脂肪族烴基，可列舉：由作為上述通式(I-A)中之X1 所表示之n價鍵結基而例示之一價～三價之脂肪族烴基及該等基經作為上述通式(I-A)中之X1 所表示之n價鍵結基之取代基而例示者取代之基所衍生之五價基中滿足特定之碳原子數者等， 作為Y14 所表示之五價之碳原子數6～35之含芳香環烴基，可列舉：由作為上述通式(I-A)中之X1 所表示之n價鍵結基而例示之一價～三價之含芳香環烴基及該等基經作為上述通式(I-A)中之X1 所表示之n價鍵結基之取代基而例示者取代之基所衍生之五價基中滿足特定之碳原子數者等， 作為Y14 所表示之五價之碳原子數2～35之含雜環之基，可列舉：由作為上述通式(I-A)中之X1 所表示之n價鍵結基而例示之一價～三價之含雜環之基及該等基經作為上述通式(I-A)中之X1 所表示之n價鍵結基之取代基而例示者取代之基所衍生之五價基中滿足特定之碳原子數者等。 作為上述通式(5)中之Y14 所表示之六價之碳原子數2～35之脂肪族烴基，可列舉：由作為上述通式(I-A)中之X1 所表示之n價鍵結基而例示之一價～三價之脂肪族烴基及該等基經作為上述通式(I-A)中之X1 所表示之n價鍵結基之取代基而例示者取代之基所衍生之六價基中滿足特定之碳原子數者等， 作為Y14 所表示之六價之碳原子數6～35之含芳香環烴基，可列舉：由作為上述通式(I-A)中之X1 所表示之n價鍵結基而例示之一價～三價之含芳香環烴基及該等基經作為上述通式(I-A)中之X1 所表示之n價鍵結基之取代基而例示者取代之基所衍生之六價基中滿足特定之碳原子數者等， 作為Y14 所表示之六價之碳原子數2～35之含雜環之基，可列舉：由作為上述通式(I-A)中之X1 所表示之n價鍵結基而例示之一價～三價之含雜環之基及該等基經作為上述通式(I-A)中之X1 所表示之n價鍵結基之取代基而例示者取代之基所衍生之六價基中滿足特定之碳原子數者等。 於上述通式(I-A)所表示之化合物中，下述通式(II-1)～(II-3)所表示者之耐熱性變高，故而較佳。 [化12]
Figure 02_image027
(式中，R82 、R83 及R84 分別獨立地表示氫原子、鹵素原子、氰基、羥基、硝基、羧基、或者有具有取代基之情形之碳原子數1～40之烷基、碳原子數6～20之芳基、碳原子數7～20之芳基烷基或碳原子數2～20之含雜環之基，R1 及R2 與上述通式(I)相同) [化13]
Figure 02_image029
(式中，r＝2～6，X2 於r＝2時為上述通式(1)所表示之基，r＝3時為上述通式(2)所表示之基，r＝4時為上述通式(3)所表示之基，r＝5時為上述通式(4)，r＝6時為上述通式(5)，R92 及R93 分別獨立地表示氫原子、鹵素原子、氰基、羥基、硝基、羧基、或者有具有取代基之情形之碳原子數1～40之烷基、碳原子數6～20之芳基、碳原子數7～20之芳基烷基或碳原子數2～20之含雜環之基，R1 及R2 與上述通式(I)相同) [化14]
Figure 02_image031
(式中，R201 、R202 、R203 、R204 、R205 、R206 、R207 、R208 分別獨立地表示氫原子、鹵素原子、氰基、羥基、硝基、羧基、有具有取代基之情形之碳原子數1～40之烷基、碳原子數6～20之芳基、碳原子數7～20之芳基烷基或碳原子數2～20之含雜環之基，Y1 、Z1 及Z2 與上述通式(1)相同) 作為上述通式(II-1)中之R82 、R83 及R84 所表示之鹵素原子、有具有取代基之情形之碳原子數1～40之烷基、碳原子數6～20之芳基、碳原子數7～20之芳基烷基、碳原子數2～20之含雜環之基，可列舉上述通式(I)中之R1 及R2 之說明中所例示者。 作為上述通式(II-2)中之R92 及R93 所表示之鹵素原子、有具有取代基之情形之碳原子數1～40之烷基、碳原子數6～20之芳基、碳原子數7～20之芳基烷基、碳原子數2～20之含雜環之基，可列舉上述通式(I)中之R1 及R2 之說明中所例示者。 作為上述通式(II-3)中之R201 、R202 、R203 、R204 、R205 、R206 、R207 、R208 所表示之鹵素原子、有具有取代基之情形之碳原子數1～40之烷基、碳原子數6～20之芳基、碳原子數7～20之芳基烷基、碳原子數2～20之含雜環之基，可列舉上述通式(I)中之R1 及R2 之說明中所例示者。 於上述通式(II-1)所表示之化合物中， 較佳為R1 為具有支鏈之碳原子數1～8之烷基、尤其為第三丁基，R2 為氫原子者；R82 、R83 及R84 分別獨立為氫原子、碳原子數1～20之烷基、碳原子數6～10之芳基、碳原子數7～12之芳基烷基、碳原子數1～10之含雜環之基，尤其R82 、R83 及R84 中之任一個為碳原子數1～4之烷基或碳原子數1～10之含雜環之基者。 於上述通式(II-2)所表示之化合物中， 較佳為R1 為具有支鏈之碳原子數1～8之烷基、尤其為第三丁基，R2 為氫原子者；R92 及R93 分別獨立為氫原子、碳原子數1～20之烷基、碳原子數6～10之芳基、碳原子數7～12之芳基烷基、碳原子數1～10之含雜環之基，尤其R92 或R93 為碳原子數1～4之烷基或碳原子數1～10之含雜環之基者。 於X2 成為上述通式(1)之情形時，Y10 較佳為硫原子、碳原子數1～20之伸烷基、碳原子數6～25之二價含芳香環烴基、碳原子數2～21之二價含雜環之基、由2,4,8,10-四氧雜螺[5,5]十一烷衍生之二價基，尤佳為碳原子數1～15之伸烷基、碳原子數6～15之二價含芳香環烴基、由2,4,8,10-四氧雜螺[5,5]十一烷衍生之二價基， Z1 及Z2 較佳為直接鍵、-CO-O-、-O-CO-、或可具有取代基之碳原子數1～20之脂肪族烴基、碳原子數6～10之芳香族烴基，尤佳為可具有取代基之碳原子數1～8之脂肪族烴基。 於X2 成為上述通式(2)之情形時，Y11 較佳為由碳原子數1～20之烷基、碳原子數6～10之芳基、碳原子數7～12之芳基烷基或碳原子數1～10之含雜環之基衍生之三價基，尤佳為由碳原子數1～8之烷基、碳原子數6～9之芳基或碳原子數1～6之含雜環之基衍生之三價基， Z1 、Z2 及Z3 較佳為與Z1 及Z2 相同， 於X2 成為上述通式(3)之情形時，Y12 較佳為與作為較佳之Y11 而於上文列舉之基對應之四價基， Z1 ～Z4 較佳為與Z1 及Z2 相同， 於X2 成為上述通式(4)之情形時，Y13 較佳為與作為較佳之Y11 而於上文列舉之基對應之五價基， Z1 ～Z5 較佳為與Z1 及Z2 相同， 於X2 成為上述通式(5)之情形時，Y14 較佳為與作為較佳之Y11 而於上文列舉之基對應之六價基， Z1 ～Z6 較佳為與Z1 及Z2 相同。 作為上述通式(I)所表示之化合物中之較佳者，可列舉下述[化14]～[化15]所示之化合物，但本發明並不限制於該等化合物。 [化15]
Figure 02_image033
[化16]
Figure 02_image035
具有上述通式(I)所表示之取代基之化合物之製造方法並無特別限定，例如可使藉由日本專利特開昭57-111375號、日本專利特開平3-173843號、日本專利特開平6-128195號、日本專利特開平7-206771號、日本專利特開平7-252191號、日本專利特表2004-501128之各公報所記載之方法而製造之酚系化合物與鹵化烯丙基化合物等進行反應而獲得。 具有上述通式(I)所表示之取代基之化合物可於本發明之感光性組合物中用作潛伏性添加劑。 上述所謂潛伏性添加劑係指於常溫、或150℃以下、例如150℃以下之預烘烤步驟中為惰性，藉由於100～250℃下加熱、或於酸/鹼觸媒存在下於80～200℃下加熱，保護基脫離而變得活性者。 於本發明之感光性組合物中，作為潛伏性添加劑之具有上述通式(I)所表示之取代基之化合物之含量於本發明之組合物之固形物成分中較佳為0.001～20質量%，更佳為0.005～5質量%。 本發明之感光性組合物係藉由光照射而性質變化之組合物，對於化學反應變得可溶者有正型抗蝕劑，對於化學反應變得不溶者有負型抗蝕劑。本發明之感光性組合物除含有具有上述通式(I)所表示之取代基之化合物作為潛伏性抗氧化劑以外，亦含有具有酸值之具有乙烯性不飽和鍵之聚合性化合物及光自由基聚合起始劑作為必須成分。 作為該具有酸值之具有乙烯性不飽和鍵之聚合性化合物，可列舉：(甲基)丙烯酸、α-氯丙烯酸、伊康酸、順丁烯二酸、甲基順丁烯二酸、反丁烯二酸、雙環庚烯二甲酸、丁烯酸、異丁烯酸、乙烯基乙酸、烯丙基乙酸、桂皮酸、山梨酸、甲基反丁烯二酸、琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、鄰苯二甲酸單[2-(甲基)丙烯醯氧基乙基]酯、ω-羧基聚己內酯單(甲基)丙烯酸酯等於兩末端具有羧基與羥基之聚合物之單(甲基)丙烯酸酯、(甲基)丙烯酸羥基乙酯-順丁烯二酸酯、(甲基)丙烯酸羥基丙酯-順丁烯二酸酯、二環戊二烯-順丁烯二酸酯或具有1個羧基與2個以上之(甲基)丙烯醯基之多官能(甲基)丙烯酸酯等不飽和多元酸；苯酚及/或甲酚酚醛清漆環氧樹脂、具有聯苯骨架、萘骨架之酚醛清漆環氧樹脂、雙酚A酚醛清漆型環氧化合物、二環戊二烯酚醛清漆型環氧化合物等酚醛清漆型環氧化合物、具有多官能環氧基之聚苯甲烷型環氧樹脂、下述通式(III)所表示之環氧化合物等使不飽和一元酸作用於環氧樹脂之環氧基之樹脂、使不飽和一元酸作用於環氧樹脂之環氧基且進而使多元酸酐作用於環氧樹脂之環氧基而獲得之樹脂、季戊四醇三丙烯酸酯、二季戊四醇五丙烯酸酯等含羥基之多官能丙烯酸酯與琥珀酸酐、鄰苯二甲酸酐、四氫鄰苯二甲酸酐等二元酸酐之反應物即具有酸值之多官能丙烯酸酯等。 [化17]
Figure 02_image037
(式中，X41 表示直接鍵、有具有取代基之情形之碳原子數1～4之伸烷基、有具有取代基之情形之碳原子數3～20之脂環式烴基、-O-、-S-、-SO2 -、-SS-、-SO-、-CO-、-OCO-或上述(1-1)～(1-3)所表示之取代基， R41 、R42 、R43 及R44 分別獨立地表示氫原子、有具有取代基之情形之碳原子數1～5之烷基、有具有取代基之情形之碳原子數1～8之烷氧基、有具有取代基之情形之碳原子數2～5之烯基或鹵素原子， m為0～10之整數) 該等具有酸值之具有乙烯性不飽和鍵之聚合性化合物可單獨使用或混合2種以上而使用，又，可與不具有酸值之具有乙烯性不飽和鍵之聚合性化合物組合而使用。於混合2種以上而使用之情形時，亦可使其等預先進行共聚而以共聚物之形式使用。 於本發明之感光性組合物中，具有酸值之具有乙烯性不飽和鍵之聚合性化合物之含量於本發明之組合物之固形物成分中較佳為20～80質量%，進而較佳為固形物成分中之30～70質量%。 作為上述不具有酸值之具有乙烯性不飽和鍵之聚合性化合物，例如可列舉：(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯、(甲基)丙烯酸縮水甘油酯、下述化合物No.A1～No.A4、(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸二甲基胺基甲酯、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸胺基丙酯、(甲基)丙烯酸二甲基胺基丙酯、(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸聚(乙氧基)乙酯、(甲基)丙烯酸丁氧基乙氧基乙酯、(甲基)丙烯酸乙基己酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸四氫呋喃酯、(甲基)丙烯酸乙烯酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸苄酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、三環癸烷二羥甲基二(甲基)丙烯酸酯、三[(甲基)丙烯醯基乙基]異氰尿酸酯、聚酯(甲基)丙烯酸酯低聚物等不飽和一元酸及多元酸或多酚之酯；(甲基)丙烯酸鋅、(甲基)丙烯酸鎂等不飽和多元酸之金屬鹽；順丁烯二酸酐、伊康酸酐、甲基順丁烯二酸酐、甲基四氫鄰苯二甲酸酐、四氫鄰苯二甲酸酐、三烷基四氫鄰苯二甲酸酐、5-(2,5-二氧代四氫呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、三烷基四氫鄰苯二甲酸酐-順丁烯二酸酐加成物、十二烯基琥珀酸酐、甲基雙環庚烯二甲酸酐等不飽和多元酸之酸酐；(甲基)丙烯醯胺、亞甲基雙-(甲基)丙烯醯胺、二伸乙基三胺三(甲基)丙烯醯胺、苯二甲基雙(甲基)丙烯醯胺、α-氯丙烯醯胺、N-2-羥基乙基(甲基)丙烯醯胺等不飽和一元酸及多元胺之醯胺；丙烯醛等不飽和醛；(甲基)丙烯腈、α-氯丙烯腈、偏氰二乙烯、氰化烯丙基等不飽和腈；苯乙烯、4-甲基苯乙烯、4-乙基苯乙烯、4-甲氧基苯乙烯、4-羥基苯乙烯、4-氯苯乙烯、二乙烯苯、乙烯基甲苯、乙烯基苯甲酸、乙烯基苯酚、乙烯基磺酸、4-乙烯基苯磺酸、乙烯基苄基甲醚、乙烯基苄基縮水甘油醚等不飽和芳香族化合物；甲基乙烯基酮等不飽和酮；乙烯胺、烯丙基胺、N-乙烯基吡咯啶酮、乙烯基哌啶等不飽和胺化合物；乙烯基甲醚、乙烯基乙醚、正丁基乙烯醚、異丁基乙烯醚、烯丙基縮水甘油醚等乙烯醚；順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺等不飽和醯亞胺類；茚、1-甲基茚等茚類；1,3-丁二烯、異戊二烯、氯戊二烯等脂肪族共軛二烯類；聚苯乙烯、聚(甲基)丙烯酸甲酯、聚(甲基)丙烯酸正丁酯、聚矽氧烷等於聚合物分子鏈之末端具有單(甲基)丙烯醯基之巨單體類；(甲基)丙烯腈、伸乙基、伸丙基、伸丁基、氯乙烯、乙酸乙烯酯等其他乙烯基化合物、及聚甲基丙烯酸甲酯巨單體、聚苯乙烯巨單體等巨單體類、三環癸烷骨架之單甲基丙烯酸酯、N-苯基順丁烯二醯亞胺、甲基丙烯醯氧基甲基-3-乙基氧雜環丁烷等與(甲基)丙烯酸之共聚物及使該等與如昭和電工股份有限公司製造之Karenz MOI、AOI之具有不飽和鍵之異氰酸酯化合物進行反應而得之(甲基)丙烯酸之共聚物、或氯乙烯、偏二氯乙烯、琥珀酸二乙烯酯、鄰苯二甲酸二烯丙酯、磷酸三烯丙酯、異氰尿酸三烯丙酯、乙烯基硫醚、乙烯基咪唑、乙烯基㗁唑啉、乙烯基咔唑、乙烯基吡咯啶酮、乙烯基吡啶、含羥基之乙烯基單體及多異氰酸酯化合物之乙烯基胺基甲酸酯化合物、含羥基之乙烯基單體及聚環氧化合物之乙烯基環氧化合物、季戊四醇三丙烯酸酯、二季戊四醇五丙烯酸酯等含羥基之多官能丙烯酸酯與甲苯二異氰酸酯、六亞甲基二異氰酸酯等多官能異氰酸酯之反應物等。 [化18]
Figure 02_image039
[化19]
Figure 02_image041
[化20]
Figure 02_image043
[化21]
Figure 02_image045
為了進行酸值調整而改良本發明之感光性組合物之顯影性，可與上述具有酸值之具有乙烯性不飽和鍵之聚合性化合物一起進而使用單官能或多官能環氧化合物。上述具有酸值之具有乙烯性不飽和鍵之聚合性化合物較佳為固形物成分之酸值為5～120 mgKOH/g之範圍，單官能或多官能環氧化合物之使用量較佳為以滿足上述酸值之方式選擇。 作為上述單官能環氧化合物，可列舉：甲基丙烯酸縮水甘油酯、甲基縮水甘油醚、乙基縮水甘油醚、丙基縮水甘油醚、異丙基縮水甘油醚、丁基縮水甘油醚、異丁基縮水甘油醚、第三丁基縮水甘油醚、戊基縮水甘油醚、己基縮水甘油醚、庚基縮水甘油醚、辛基縮水甘油醚、壬基縮水甘油醚、癸基縮水甘油醚、十一烷基縮水甘油醚、十二烷基縮水甘油醚、十三烷基縮水甘油醚、十四烷基縮水甘油醚、十五烷基縮水甘油醚、十六烷基縮水甘油醚、2-乙基己基縮水甘油醚、烯丙基縮水甘油醚、炔丙基縮水甘油醚、對甲氧基乙基縮水甘油醚、苯基縮水甘油醚、對甲氧基縮水甘油醚、對丁基苯酚縮水甘油醚、甲苯基縮水甘油醚、2-甲基甲苯基縮水甘油醚、4-壬基苯基縮水甘油醚、苄基縮水甘油醚、對異丙苯基苯基縮水甘油醚、三苯甲基縮水甘油醚、甲基丙烯酸2,3-環氧丙酯、環氧化大豆油、環氧化亞麻仁油、丁酸縮水甘油酯、一氧化乙烯基環己烷、1,2-環氧基-4-乙烯基環己烷、氧化苯乙烯、氧化蒎烯、氧化甲基苯乙烯、環氧環己烷、環氧丙烷等。 作為上述多官能環氧化合物，若使用選自由雙酚型環氧化合物及縮水甘油醚類所組成之群中之一種以上，則可獲得特性更良好之感光性組合物，故而較佳。作為該雙酚型環氧化合物，除可使用上述通式(III)所表示之環氧化合物以外，亦可使用例如氫化雙酚型環氧化合物等雙酚型環氧化合物。作為該縮水甘油醚類，可列舉：乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、1,4-丁二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、1,8-辛二醇二縮水甘油醚、1,10-癸二醇二縮水甘油醚、2,2-二甲基-1,3-丙二醇二縮水甘油醚、二乙二醇二縮水甘油醚、三乙二醇二縮水甘油醚、四乙二醇二縮水甘油醚、六乙二醇二縮水甘油醚、1,4-環己烷二甲醇二縮水甘油醚、1,1,1-三(縮水甘油氧基甲基)丙烷、1,1,1-三(縮水甘油氧基甲基)乙烷、1,1,1-三(縮水甘油氧基甲基)甲烷、1,1,1,1-四(縮水甘油氧基甲基)甲烷。 此外，亦可使用苯酚酚醛清漆型環氧化合物、聯苯酚醛清漆型環氧化合物、甲酚酚醛清漆型環氧化合物、雙酚A酚醛清漆型環氧化合物、二環戊二烯酚醛清漆型環氧化合物等酚醛清漆型環氧化合物；3,4-環氧基-6-甲基環己基甲基-3,4-環氧基-6-甲基環己烷羧酸酯、3,4-環氧環己基甲基-3,4-環氧環己烷羧酸酯、1-環氧乙基-3,4-環氧環己烷等脂環式環氧化合物；鄰苯二甲酸二縮水甘油酯、四氫鄰苯二甲酸二縮水甘油酯、二聚酸縮水甘油酯等縮水甘油酯類；四縮水甘油基二胺基二苯基甲烷、三縮水甘油基對胺基苯酚、N,N-二縮水甘油基苯胺等縮水甘油胺類；1,3-二縮水甘油基-5,5-二甲基乙內醯脲、異氰尿酸三縮水甘油酯等雜環式環氧化合物；二氧化二環戊二烯等二氧化物化合物；萘型環氧化合物、三苯基甲烷型環氧化合物、二環戊二烯型環氧化合物等。 上述光自由基聚合起始劑只要為藉由受到光照射而能夠使自由基聚合開始之化合物即可，例如可例示苯乙酮系化合物、苯偶醯系化合物、二苯甲酮系化合物、9-氧硫𠮿
Figure 106110457-xxxx-3
系化合物等酮系化合物、肟系化合物等作為較佳者。 作為苯乙酮系化合物，例如可列舉：二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、4'-異丙基-2-羥基-2-甲基苯丙酮、2-羥基甲基-2-甲基苯丙酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、對二甲基胺基苯乙酮、對第三丁基二氯苯乙酮、對第三丁基三氯苯乙酮、對疊氮苯亞甲基苯乙酮、1-羥基環己基苯基酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙酮-1、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮-1、安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香正丁醚、安息香異丁醚、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙烷-1-酮等。 作為苯偶醯系化合物，可列舉苯偶醯、茴香偶醯等。 作為二苯甲酮系化合物，例如可列舉：二苯甲酮、鄰苯甲醯基苯甲酸甲酯、米其勒酮、4,4'-雙二乙基胺基二苯甲酮、4,4'-二氯二苯甲酮、4-苯甲醯基-4'-甲基二苯硫醚等。 作為9-氧硫𠮿
Figure 106110457-xxxx-3
系化合物，可列舉：9-氧硫𠮿
Figure 106110457-xxxx-3
、2-甲硫基𠮿酮、2-乙基-9-氧硫𠮿
Figure 106110457-xxxx-3
、2-氯-9-氧硫𠮿
Figure 106110457-xxxx-3
、2-異丙硫基𠮿酮、2,4-二乙基-9-氧硫𠮿
Figure 106110457-xxxx-3
等。 作為肟系化合物，尤其下述通式(IV)或(V)所表示之化合物就感度及耐熱性之方面而言較佳。 [化22]
Figure 02_image047
(式中，R51 及R52 分別獨立地表示氫原子、氰基、有具有取代基之情形之碳原子數1～20之烷基、有具有取代基之情形之碳原子數6～30之芳基、有具有取代基之情形之碳原子數7～30之芳基烷基或有具有取代基之情形之碳原子數2～20之含雜環之基， R53 及R54 分別獨立地表示鹵素原子、硝基、氰基、羥基、羧基、R55 、OR56 、SR57 、NR58 R59 、COR60 、SOR61 、SO2 R62 或CONR63 R64 ，R53 及R54 有相互鍵結而形成環之情形， R55 、R56 、R57 、R58 、R59 、R60 、R61 、R62 、R63 及R64 分別獨立地表示有具有取代基之情形之碳原子數1～20之烷基、有具有取代基之情形之碳原子數6～30之芳基、有具有取代基之情形之碳原子數7～30之芳基烷基或有具有取代基之情形之碳原子數2～20之含雜環之基， X3 表示氧原子、硫原子、硒原子、CR75 R76 、CO、NR77 或PR78 ， X4 表示單鍵或CO， R75 ～R78 表示碳原子數1～20之烷基、碳原子數6～30之芳基或碳原子數7～30之芳基烷基，該烷基或芳基烷基中之亞甲基既有被取代為鹵素原子、硝基、氰基、羥基、羧基或含雜環之基之情形，有被取代為-O-之情形， R53 及R54 有分別獨立地與鄰接之任一苯環成為一體而形成環之情形， a表示0～4之整數， b表示0～5之整數) [化23]
Figure 02_image049
(式中，R101 及R102 分別獨立地表示R111 、OR111 、COR111 、SR111 、CONR112 R113 或CN， R111 、R112 及R113 分別獨立地表示氫原子、碳原子數1～20之烷基、碳原子數6～30之芳基、碳原子數7～30之芳基烷基或碳原子數2～20之含雜環之基， R111 、R112 及R113 所表示之基之氫原子有進而經R121 、OR121 、COR121 、SR121 、NR122 R123 、CONR122 R123 、-NR122 -OR123 、-NCOR122 -OCOR123 、NR122 COR121 、OCOR121 、COOR121 、SCOR121 、OCSR121 、COSR121 、CSOR121 、羥基、硝基、CN或鹵素原子取代之情形， R121 、R122 及R123 分別獨立地表示氫原子、碳原子數1～20之烷基、碳原子數6～30之芳基、碳原子數7～30之芳基烷基或碳原子數2～20之含雜環之基， R121 、R122 及R123 所表示之基之氫原子有進而經羥基、硝基、CN、鹵素原子、羥基或羧基取代之情形， R111 、R112 、R113 、R121 、R122 及R123 所表示之基之伸烷基部分有於氧原子不相鄰之條件下1～5次被取代為-O-、-S-、-COO-、-OCO-、-NR124- 、-NR124 COO-、-OCONR124- 、-SCO-、-COS-、-OCS-或-CSO-之情形， R124 表示氫原子、碳原子數1～20之烷基、碳原子數6～30之芳基、碳原子數7～30之芳基烷基或碳原子數2～20之含雜環之基， R111 、R112 、R113 、R121 、R122 、R123 及R124 所表示之基之烷基部分既有具有分支側鏈之情形，亦有為環狀烷基之情形， R103 表示氫原子、碳原子數1～20之烷基、碳原子數6～30之芳基、碳原子數7～30之芳基烷基或碳原子數2～20之含雜環之基，R103 所表示之基之烷基部分既有具有分支側鏈之情形，亦有為環狀烷基之情形，又，R103 與R107 、R103 與R108 、R104 與R105 、R105 與R106 及R106 與R107 有分別成為一體而形成環之情形， R103 所表示之基之氫原子有進而經R121 、OR121 、COR121 、SR121 、NR122 R123 、CONR122 R123 、-NR122 -OR123 、-NCOR122 -OCOR123 、NR122 COR121 、OCOR121 、COOR121 、SCOR121 、OCSR121 、COSR121 、CSOR121 、羥基、硝基、CN、鹵素原子、或COOR121 取代之情形， R104 、R105 、R106 及R107 分別獨立地表示R111 、OR111 、SR111 、COR114 、CONR151 R116 、NR112 COR111 、OCOR111 、COOR114 、SCOR111 、OCSR111 、COSR114 、CSOR111 、羥基、CN或鹵素原子，R104 與R105 、R105 與R106 及R106 與R107 有分別成為一體而形成環之情形， R114 、R115 及R116 表示氫原子或碳原子數1～20之烷基， R108 表示R111 、OR111 、SR111 、COR111 、CONR112 R113 、NR112 COR111 、OCOR111 、COOR111 、SCOR111 、OCSR111 、COSR111 、CSOR111 、羥基、CN或鹵素原子， w表示0或1) 作為其他光自由基聚合起始劑，可列舉：2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(環戊二烯基)-雙[2,6-二氟-3-( pyl-1-基)]鈦等。 該等光自由基聚合起始劑可對應於所需之性能調配1種或2種以上者而使用。 如上之光自由基聚合起始劑之含量於本發明之感光性組合物之固形物成分中較佳為0.1～30質量%，尤佳為0.5～10質量%。若上述光自由基聚合起始劑之含量小於0.1質量%，則有利用曝光之硬化變得不充分之情形，若大於30質量%，則有於感光性組合物中析出起始劑之情形。 本發明之感光性組合物亦可進而添加著色劑而製成著色感光性組合物。該著色感光性組合物之硬化物可適宜地用作彩色濾光片。 於本發明之著色感光性組合物中，著色劑之添加量於本發明之著色感光性組合物之固形物成分中較佳為0.01～50質量%，更佳為0.1～30質量%。若上述著色劑之含量小於0.01質量%，則有無法獲得所需之色度之情形，若大於50質量%，則有於著色感光性組合物中析出著色劑之情形。 作為上述著色劑，可列舉染料或顏料。 作為染料，只要為於380～1200 nm具有吸收之化合物，則無特別限定，例如可列舉：偶氮化合物、蒽醌化合物、靛藍化合物、三芳基甲烷化合物、𠮿
Figure 106110457-xxxx-3
化合物、茜素化合物、吖啶化合物、茋化合物、噻唑化合物、萘酚化合物、喹啉化合物、硝基化合物、吲達胺化合物、㗁 𠯤化合物、酞菁化合物、花青化合物、二亞銨化合物、氰基乙烯基化合物、二氰基苯乙烯化合物、玫瑰紅化合物、苝化合物、多烯萘內醯胺化合物、香豆素化合物、方酸鎓化合物、克酮鎓化合物、螺吡喃化合物、螺㗁 𠯤化合物、部花青化合物、氧喏化合物、苯乙烯基化合物、吡喃鎓化合物、繞丹寧化合物、㗁唑啉酮化合物、鄰苯二甲醯亞胺化合物、㖕啉化合物、萘醌化合物、氮雜蒽醌化合物、卟啉化合物、氮雜卟啉化合物、吡咯亞甲基化合物、喹吖啶酮化合物、吡咯并吡咯二酮化合物、靛青化合物、吖啶化合物、吖𠯤化合物、甲亞胺化合物、苯胺化合物、喹吖啶酮化合物、喹酞酮化合物、醌亞胺化合物、銥錯合物化合物、銪錯合物化合物等染料等，該等亦可混合複數種而使用。 作為顏料，可使用無機顏料或有機顏料，例如可使用：亞硝基化合物、硝基化合物、偶氮化合物、二偶氮化合物、𠮿
Figure 106110457-xxxx-3
化合物、喹啉化合物、蒽醌化合物、香豆素化合物、酞菁化合物、異吲哚啉酮化合物、異吲哚啉化合物、喹吖啶酮化合物、蒽締蒽酮化合物、哌瑞酮化合物、苝化合物、吡咯并吡咯二酮化合物、硫靛化合物、二㗁 𠯤化合物、三苯基甲烷化合物、喹酞酮化合物、萘四羧酸；偶氮染料、花青染料之金屬錯合物化合物；色澱顏料；；利用環氧樹脂調整、被覆上述碳黑而得者、利用樹脂將上述碳黑預先於溶劑中進行分散處理並吸附20～200 mg/g之樹脂而得者、將上述碳黑進行酸性或鹼性表面處理而得者、平均粒徑為8 nm以上且DBP吸油量為90 ml/100 g以下者、由950℃下之揮發成分中之CO、CO2 算出之總氧量相對於碳黑之每表面積100 m2 為9 mg以上者；石墨、石墨化碳黑、活性碳、碳纖維、奈米碳管、螺旋碳纖維、碳奈米角、碳氣凝膠、富勒烯；苯胺黑、顏料黑7、鈦黑；疏水性樹脂、氧化鉻綠、米洛麗藍、鈷綠、鈷藍、錳系、亞鐵氰化物、磷酸鹽群青、鐵藍、群青、天藍、濃綠、翡翠綠、硫酸鉛、鉛黃、鋅黃、鐵丹(氧化鐵紅(III))、鎘紅、合成鐵黑、棕土等無機含量或有機顏料。該等顏料可單獨或混合複數種而使用。 作為上述無機顏料或有機顏料，亦可使用市售之顏料，例如可列舉：顏料紅1、2、3、9、10、14、17、22、23、31、38、41、48、49、88、90、97、112、119、122、123、144、149、166、168、169、170、171、177、179、180、184、185、192、200、202、209、215、216、217、220、223、224、226、227、228、240、254；顏料橙13、31、34、36、38、43、46、48、49、51、52、55、59、60、61、62、64、65、71；顏料黃1、3、12、13、14、16、17、20、24、55、60、73、81、83、86、93、95、97、98、100、109、110、113、114、117、120、125、126、127、129、137、138、139、147、148、150、151、152、153、154、166、168、175、180、185；顏料綠7、10、36；顏料藍15、15：1、15：2、15：3、15：4、15：5、15：6、22、24、56、60、61、62、64；顏料紫1、19、23、27、29、30、32、37、40、50等。 於本發明之感光性組合物及著色感光性組合物中可進而添加溶劑。作為該溶劑，可列舉通常能夠視需要將上述各成分溶解或分散之溶劑，例如可列舉：甲基乙基酮、甲基戊基酮、二乙基酮、丙酮、甲基異丙基酮、甲基異丁基酮、環己酮、2-庚酮等酮類；乙醚、二㗁烷、四氫呋喃、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、二丙二醇二甲醚等醚系溶劑；乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸環己酯、乳酸乙酯、琥珀酸二甲酯、TEXANOL等酯系溶劑；乙二醇單甲醚、乙二醇單乙醚等溶纖劑系溶劑；甲醇、乙醇、異或正丙醇、異或正丁醇、戊醇、二丙酮醇等醇系溶劑；乙二醇單甲基乙酸酯、乙二醇單乙基乙酸酯、丙二醇-1-單甲醚-2-乙酸酯(PGMEA)、二丙二醇單甲醚乙酸酯、乙酸3-甲氧基丁酯、丙酸乙氧基乙酯、1-第三丁氧基-2-丙醇、乙酸3-甲氧基丁酯、環己醇乙酸酯等醚酯系溶劑；苯、甲苯、二甲苯等BTX系溶劑；己烷、庚烷、辛烷、環己烷等脂肪族烴系溶劑；松節油、D-檸檬烯、蒎烯等萜烯系烴油；礦油精、Swazol＃310(Cosmo Matsuyama Oil股份有限公司)、Solvesso＃100(Exxon Chemical股份有限公司)等石蠟系溶劑；四氯化碳、氯仿、三氯乙烯、二氯甲烷、1,2-二氯乙烷等鹵代脂肪族烴系溶劑；氯苯等鹵代芳香族烴系溶劑；卡必醇系溶劑、苯胺、三乙胺、吡啶、乙酸、乙腈、二硫化碳、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮、二甲基亞碸、水等，該等溶劑可作為1種或2種以上之混合溶劑而使用。於該等中，酮類、醚酯系溶劑等、尤其丙二醇-1-單甲醚-2-乙酸酯、環己酮等於感光性組合物中，使抗蝕劑與光自由基聚合起始劑之相溶性良好，故而較佳。於使用溶劑之情形時，就操作性等觀點而言，較佳為以本發明之感光性組合物或著色感光性組合物之固形物成分成為25～35質量%之量使用。 於本發明之感光性組合物及著色感光性組合物中可進而含有無機化合物。作為該無機化合物，例如可列舉：氧化鎳、氧化鐵、氧化銥、氧化鈦、氧化鋅、氧化鎂、氧化鈣、氧化鉀、二氧化矽、氧化鋁等金屬氧化物；層狀黏土礦物、米洛麗藍、碳酸鈣、碳酸鎂、鈷系、錳系、玻璃粉末、雲母、滑石、高嶺土、亞鐵氰化物、各種金屬硫酸鹽、硫化物、硒化物、矽酸鋁、矽酸鈣、氫氧化鋁、鉑、金、銀、銅等。 於在本發明之感光性組合物及著色感光性組合物中使用顏料等著色劑及/或無機化合物之情形時，可添加分散劑。作為該分散劑，只要為可使著色劑、無機化合物分散、穩定化者，則無特別限制，可使用市售之分散劑、例如BYK-Chemie公司製造之BYK系列等，可適宜地使用包含具有鹼性官能基之聚酯、聚醚、聚胺基甲酸酯之高分子分散劑、具有氮原子作為鹼性官能基且具有氮原子之官能基為胺及/或其四級鹽且胺值為1～100 mgKOH/g者。 又，於本發明之感光性組合物及著色感光性組合物中，可視需要添加對大茴香醚、對苯二酚、鄰苯二酚、第三丁基鄰苯二酚、啡噻𠯤等熱聚合抑制劑；塑化劑；接著促進劑；填充劑；消泡劑；調平劑；表面調整劑；酚系抗氧化劑、亞磷酸酯系抗氧化劑、硫醚系抗氧化劑等抗氧化劑；紫外線吸收劑；分散助劑；凝聚防止劑；觸媒；效果促進劑；交聯劑；增黏劑等慣用之添加物。 又，藉由一起使用上述具有酸值之具有乙烯性不飽和鍵之聚合性化合物與其他有機聚合物，亦可改善本發明之感光性組合物及著色感光性組合物之硬化物之特性。作為上述有機聚合物，例如可列舉：聚苯乙烯、聚甲基丙烯酸甲酯、甲基丙烯酸甲酯-丙烯酸乙酯共聚物、聚(甲基)丙烯酸、苯乙烯-(甲基)丙烯酸共聚物、(甲基)丙烯酸-甲基丙烯酸甲酯共聚物、乙烯-氯乙烯共聚物、乙烯-乙烯基共聚物、聚氯乙烯樹脂、ABS樹脂、尼龍6、尼龍66、尼龍12、胺基甲酸酯樹脂、聚碳酸酯聚乙烯丁醛、纖維素酯、聚丙烯醯胺、飽和聚酯、酚樹脂、苯氧基樹脂、聚醯胺醯亞胺樹脂、聚醯胺酸樹脂、環氧樹脂等，於該等中，亦較佳為聚苯乙烯、(甲基)丙烯酸-甲基丙烯酸甲酯共聚物、環氧樹脂。 於本發明之感光性組合物及著色感光性組合物中可進而併用鏈轉移劑、增感劑、界面活性劑、矽烷偶合劑、三聚氰胺化合物等。 作為上述鏈轉移劑、增感劑，一般使用含硫原子之化合物。例如可列舉：硫代乙醇酸、硫代蘋果酸、硫代水楊酸、2-巰基丙酸、3-巰基丙酸、3-巰基丁酸、N-(2-巰基丙醯基)甘胺酸、2-巰基煙鹼酸、3-[N-(2-巰基乙基)胺甲醯基]丙酸、3-[N-(2-巰基乙基)胺基]丙酸、N-(3-巰基丙醯基)丙胺酸、2-巰基乙磺酸、3-巰基丙磺酸、4-巰基丁磺酸、十二烷基(4-甲硫基)苯醚、2-巰基乙醇、3-巰基-1,2-丙二醇、1-巰基-2-丙醇、3-巰基-2-丁醇、巰基苯酚、2-巰基乙基胺、2-巰基咪唑、2-巰基苯并咪唑、2-巰基-3-吡啶醇、2-巰基苯并噻唑、巰基乙酸、三羥甲基丙烷三(3-巰基丙酸酯)、季戊四醇四(3-巰基丙酸酯)等巰基化合物、將該巰基化合物進行氧化而獲得之二硫醚化合物、碘乙酸、碘丙酸、2-碘乙醇、2-碘乙磺酸、3-碘丙磺酸等碘化烷基化合物、三羥甲基丙烷三(3-巰基異丁酸酯)、丁二醇雙(3-巰基異丁酸酯)、己二硫醇、癸二硫醇、1,4-二甲基巰基苯、丁二醇雙巰基丙酸酯、丁二醇雙巰基乙酸酯、乙二醇雙巰基乙酸酯、三羥甲基丙烷三巰基乙酸酯、丁二醇雙巰基丙酸酯、三羥甲基丙烷三巰基丙酸酯、三羥甲基丙烷三巰基乙酸酯、季戊四醇四巰基丙酸酯、季戊四醇四巰基乙酸酯、三羥基乙基三巰基丙酸酯、下述化合物No.C1、三巰基丙酸三(2-羥基乙基)異氰尿酸酯等脂肪族多官能硫醇化合物、昭和電工公司製造之Karenz MT BD1、PE1、NR1等。 [化24]
Figure 02_image051
作為上述界面活性劑，可使用全氟烷基磷酸酯、全氟烷基羧酸鹽等氟界面活性劑、高級脂肪酸鹼金屬鹽、烷基磺酸鹽、烷基硫酸鹽等陰離子系界面活性劑、高級胺氫鹵酸鹽、四級銨鹽等陽離子系界面活性劑、聚乙二醇烷基醚、聚乙二醇脂肪酸酯、山梨醇酐脂肪酸酯、脂肪酸單甘油酯等非離子界面活性劑、兩性界面活性劑、聚矽氧系界面活性劑等界面活性劑，該等亦可組合使用。 作為上述矽烷偶合劑，例如可使用信越化學公司製造之矽烷偶合劑，其中，適宜使用KBE-9007、KBM-502、KBE-403等具有異氰酸基、甲基丙烯醯基、環氧基之矽烷偶合劑。 作為上述三聚氰胺化合物，可列舉(聚)羥甲基三聚氰胺、(聚)羥甲基甘脲、(聚)羥甲基苯胍胺、(聚)羥甲基脲等氮化合物中之活性羥甲基(CH2 OH基)之全部或一部分(至少2個)經烷基醚化之化合物。此處，作為構成烷基醚之烷基，可列舉甲基、乙基或丁基，既有相互相同之情形，亦有不同之情形。又，未經烷基醚化之羥甲基既有於一分子內進行自縮合之情形，亦有於兩分子間進行縮合，結果形成低聚物成分之情形。具體而言，可使用六甲氧基甲基三聚氰胺、六丁氧基甲基三聚氰胺、四甲氧基甲基甘脲、四丁氧基甲基甘脲等。於該等中，較佳為六甲氧基甲基三聚氰胺、六丁氧基甲基三聚氰胺等經烷基醚化之三聚氰胺。 本發明之感光性組合物及著色感光性組合物可藉由旋轉塗佈機、輥式塗佈機、棒式塗佈機、模嘴塗佈機、簾幕式塗佈機、各種印刷、浸漬等公知手段而應用於鈉玻璃、石英玻璃、半導體基板、金屬、紙、塑膠等支持基體上。又，亦可於暫時施加至膜等支持基體上後轉印至其他支持基體上，其應用方法並無限制。 又，作為使本發明之感光性組合物及著色感光性組合物硬化時所使用之活性光之光源，可使用發出波長300～450 nm之光者，例如可使用超高壓水銀、水銀蒸汽弧、碳弧、氙弧等。 進而，藉由曝光光源使用雷射光，不使用遮罩而由電腦等之數位資訊直接形成圖像之雷射直接繪圖法不僅實現生產性之提高，而且亦實現解像性或位置精度等之提高，因此較為有用，作為該雷射光，適宜使用340～430 nm之波長之光，亦使用氬離子雷射、氦氖雷射、YAG雷射、及半導體雷射等發出可見光至紅外線區域之光者。於使用該等雷射之情形時，添加吸收可見光至紅外線之該區域之增感色素。 本發明之感光性組合物及著色感光性組合物亦可經過使用兩種感光性組合物或著色感光性組合物分成兩次進行圖案化之雙重圖案化製程而進行圖案化。 使本發明之感光性組合物或著色感光性組合物硬化之方法包括如下步驟：藉由上述旋轉塗佈機、輥式塗佈機、棒式塗佈機、模嘴塗佈機、簾幕式塗佈機、各種印刷、浸漬等公知手段，塗佈於鈉玻璃、石英玻璃、半導體基板、金屬、紙、塑膠等支持基體上而形成塗膜；及對該塗膜曝光上述活性光而使之硬化。 本發明之感光性組合物及著色感光性組合物(或其硬化物)可用於光硬化性塗料或清漆、光硬化性接著劑等接著劑、印刷基板、或彩色電視、PC監視器、攜帶型資訊終端、數位相機等彩色顯示之液晶顯示面板之彩色濾光片、CCD影像感測器之彩色濾光片、感光性間隔件、黑管柱間隔件、電漿顯示面板用電極材料、觸控面板、觸控感測器、粉末塗層、印刷油墨、印刷版、牙科用組合物、光造形用樹脂、凝膠塗層、電子工學用光阻劑、電鍍抗蝕劑、蝕刻阻劑、液狀及乾燥膜之兩者、阻焊劑、用以製造各種顯示用途用彩色濾光片之或於電漿顯示面板、電發光顯示裝置及LCD之製造步驟中用以形成構造之抗蝕劑、用以封入電氣及電子零件之組合物、阻焊劑、磁記錄材料、微小機械零件、波導、光開關、鍍覆用遮罩、蝕刻遮罩、彩色試驗系、玻璃纖維纜線塗層、網版印刷用模板、用以藉由立體微影而製造三維物體之材料、全像記錄用材料、圖像記錄材料、微細電子電路、脫色材料、用於圖像記錄材料之脫色材料、使用微膠囊之圖像記錄材料用脫色材料、印刷配線板用光阻劑材料、UV及可見光雷射直接圖像系用光阻劑材料、用於印刷電路基板之逐次積層中之介電體層形成之光阻劑材料、3D安裝用光阻劑材料或保護膜等各種用途，其用途並無特別限制。 本發明之感光性組合物可藉由使其硬化而用作透明構造體。作為透明構造體，例如可列舉：被稱為感光性間隔件(PS)、管柱間隔件(CS)之柱形物；(奈米)壓印之微細圖案；大型廣告看板等之製造或液晶顯示器用彩色濾光片或配向膜之印刷等電子裝置製造所使用之噴墨接受層等。本發明之透明構造體適宜用於顯示裝置。 本發明之感光性組合物可用於透明導電膜、反射膜、偏光板、保護膜等，可用作藉由如下方式積層之透明積層體，即，於透明基板依序塗佈所需之各層，隔著具有特定之圖案形狀之遮罩照射活性光，利用顯影液使曝光後之覆膜顯影，並對顯影後之覆膜進行加熱。作為透明積層體，例如可列舉於透明基材交替地形成有包含氧化銦與氧化鈰之複合氧化物之透明薄膜層與金屬薄膜層者等。可於上述各層之各者使用含有具有通式(I)所表示之取代基之化合物作為潛伏性添加劑的本發明之感光性組合物，亦可於任一層使用該感光性組合物。又，進而，該透明積層體適宜用於顯示裝置。 本發明之著色感光性組合物係以形成彩色濾光片之像素為目的而使用，尤其作為用以形成液晶顯示面板等圖像顯示裝置用顯示裝置用彩色濾光片之感光性組合物較為有用。 上述顯示裝置用彩色濾光片藉由如下步驟而較佳地形成：(1)於基板上形成本發明之著色感光性組合物之塗膜；(2)隔著具有特定之圖案形狀之遮罩對該塗膜照射活性光；(3)利用顯影液使曝光後之覆膜顯影；(4)對顯影後之該覆膜進行加熱。又，本發明之著色感光性組合物作為無顯影步驟之噴墨方式之著色感光性組合物亦有用。 作為上述遮罩，亦可使用半色調遮罩或灰度遮罩等多階遮罩。 其次，對本發明之新穎化合物進行說明。本發明之新穎化合物係由下述結構中之任一者表示。 [化25]
Figure 02_image053
[化26]
Figure 02_image055
[化27]
Figure 02_image057
本發明之新穎化合物之製造方法並無特別限定，例如可使藉由日本專利特開昭57-111375號、日本專利特開平3-173843號、日本專利特開平6-128195號、日本專利特開平7-206771號、日本專利特開平7-252191號、日本專利特表2004-501128號之各公報所記載之方法而製造之酚系化合物與鹵化烯丙基化合物等進行反應而獲得。 本發明之新穎化合物可用於潛伏性抗氧化劑、潛伏性紫外線吸收劑、溶解調整劑等。 [實施例] 以下，列舉實施例等更詳細地說明本發明，但本發明並不限定於該等實施例等。 [實施例1-1]化合物No.1之合成 於下述化合物No.1'之酚化合物1當量之二甲基乙醯胺溶液(理論產量之3倍量)中添加碳酸鉀(相對於1個酚基為2當量)，於室溫下攪拌30分鐘。添加烯丙基溴(相對於1個酚基為1.5當量)，於60℃下攪拌5小時。添加乙酸乙酯，利用1%鹽酸溶液洗淨後進行油水分離，利用無水硫酸鈉將有機層乾燥後，將溶劑蒸餾去除，進行晶析。於60℃下使所獲得之固體減壓乾燥3小時，獲得目標物。藉由1 H-NMR、IR確認所獲得之固體為目標物。將結果示於[表1]～[表2]。 [實施例1-2～1-6]化合物No.2～6之合成 於實施例1-1中，使用下述化合物No.2'～6'之酚化合物代替下述化合物No.1'之酚化合物，除此以外，以與實施例1-1相同之方式合成作為目標物之化合物No.2～6。藉由1 H-NMR、IR確認所獲得之固體為目標物。將結果示於[表1]～[表2]。 [化28]
Figure 02_image059
[化29]
Figure 02_image061
[表1]
Figure 106110457-A0304-0001
 [表2]
Figure 106110457-A0304-0002
 [實施例2-1～2-2及比較例2-1～2-3]感光性組合物No.1～No.2及比較感光性組合物No.1～No.3之製備 將SPC-1000(昭和電工公司製造，固形物成分29%之PGMEA溶液)50.0 g、ARONIX M-450(東亞合成公司製造)11.6 g、NCI-930(ADEKA公司製造)0.3 g、PGMEA34.7 g、FZ2122(Dow Corning Toray公司製造，固形物成分1%之PGMEA溶液)2.9 g及[表3]所記載之化合物0.81 g進行混合，攪拌至不溶物消失，獲得感光性組合物No.1～No.2及比較感光性組合物No.1～No.3。 [表3]
Figure 106110457-A0304-0003
 [化30]
Figure 02_image063
[化31]
Figure 02_image065
[化32]
Figure 02_image067
[評價例1-1及比較評價例1-1]釋氣評價 將化合物No.1、化合物No.2以及比較化合物No.2分別稱取5 mg，利用熱質量測定裝置自室溫升溫(20℃/min.)至230℃後，測定於230℃下保持30分鐘之時間點之重量減少率，作為感光性組合物No.1～No.2及比較感光性組合物No.2之釋氣評價。重量減少越小，表示釋氣越少。將結果示於[表4]。 [表4]
Figure 106110457-A0304-0004
 由上述結果可知，本發明之化合物之釋氣較少，含有本發明之化合物之本發明之感光性組合物之釋氣變少。 [評價例2-1及比較評價例2-1～2-2]耐溶劑性評價 將上述實施例2-1中所獲得之感光性組合物No.1及比較例2-1及2-3中所獲得之比較感光性組合物No.1及No.3分別於410 rpm×7秒之條件下塗敷至玻璃基板，利用加熱板使其乾燥(90℃×90秒)。利用超高壓水銀燈對所獲得之塗膜進行曝光(40 mJ/cm2 )。將曝光後之塗膜於230℃×30分鐘之條件下進行焙燒。測定所獲得之塗膜之膜厚後，於室溫下於PGMEA、環己酮、N-甲基吡咯啶酮、N-乙基吡咯啶酮中浸漬30分鐘，測定浸漬後之膜厚。浸漬前後之膜厚比(浸漬後之膜厚×100/浸漬前之膜厚)越接近100%，耐溶劑性評價為越高。 [表5]
Figure 106110457-A0304-0005
 由[表5]可知，與不含抗氧化劑之比較感光性組合物No.3之硬化物相比，先前之含有酚系抗氧化劑之比較感光性組合物No.1之硬化物之耐溶劑性降低，但使用本案之化合物作為潛伏性添加劑之感光性組合物No.1維持與不含抗氧化劑之情形相同之耐溶劑性。 由以上之結果可知，使用本發明之化合物作為潛伏性添加劑之感光性組合物之釋氣較少，其硬化物之耐溶劑性優異。 [產業上之可利用性] 根據本發明，可提供一種使用於常溫下為惰性，藉由加熱至特定溫度使之活化而表現出作為抗氧化劑或紫外線吸收劑之功能的化合物之釋氣較少且硬化物之耐溶劑性較高之感光性組合物。Hereinafter, the present invention will be described in detail based on preferred embodiments. The photosensitive composition of this invention contains the compound which has the substituent represented by the said general formula (I). Among the compounds having the substituent represented by the above-mentioned general formula (I), those represented by the following general formula (IA) are particularly preferable because they have higher heat resistance and less outgassing. [hua 2]
Figure 02_image007
(in the formula, n represents an integer of 1 to 10, X 1 represents an n-valent bonding group, and R 1 , R 2 and j are the same as those of the general formula (I) above.) The halogen atom represented by R 1 and R 2 may be Examples include fluorine, chlorine, bromine, and iodine, and examples of the alkyl group having 1 to 20 carbon atoms represented by R 1 and R 2 include methyl, ethyl, propyl, isopropyl, butyl, and second butyl. , tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, 3-heptyl, 1-octyl, isooctyl, 3-octyl, adamantyl, etc., as the number of carbon atoms represented by R 1 and R 2 The aryl groups of 6 to 20 include: phenyl, naphthyl, anthracenyl, phenanthryl, indenyl, indenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4 -Vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexylbenzene phenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4-(2-ethylhexyl)phenyl, 4-stearylphenyl, 2,3-dimethylphenyl, 2,4- Dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-dimethylphenyl Di-tert-butylphenyl, 2,5-di-tert-butylphenyl, 2,6-di-tert-butylphenyl, 2,4-di-tert-pentylphenyl, 2,5-di-tertiary Tripentylphenyl, 2,5-di-tert-octylphenyl, 2,4-dicumylphenyl, 4-cyclohexylphenyl, (1,1'-biphenyl)-4-yl , 2,4,5-trimethylphenyl, ferrocene, etc. Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R 1 and R 2 include benzyl, 1-methyl -1-phenylethyl, 1-naphthylmethyl, 9-anthrylmethyl, 9-intenyl, 3-phenylpropyl, methyl-2-phenylpropan-2-yl, diphenyl A methyl group, a triphenylmethyl group, a phenethyl group, a styryl group, a cinnamyl group, etc., as the C 2-20 heterocyclic ring-containing group represented by R 1 and R 2 include: a pyridine ring , pyrimidine, pyridine, piperidine, pyran, pyrazoline, tris, pyrroline, quinoline, isoquinoline, imidazoline, benzimidazoline, triazole Line ring, furan ring, benzofuran ring, thiadiazoline ring, thiazoline ring, benzothiazoline ring, thiophene ring, oxazoline ring, benzoxazoline ring, isothiazoline ring, isoxazole A group formed by combining a heterocyclic ring such as a morphine ring, an indole ring, a pyrrolidine ring, a piperidone ring, a dioxane ring, etc. with a methylene chain, as the trialkylsilyl group represented by R 1 and R 2 , can be Examples include: trimethylsilane, triethylsilane, ethyldimethylsilane and other silane groups substituted with alkyl groups having 1 to 6 carbon atoms (the three alkyl groups are the same or different). Examples of the alkyl group having 1 to 8 carbon atoms represented by R' include those satisfying a specific number of carbon atoms among the above-mentioned alkyl groups represented by R 1 . As the substitution R 1 and R 2 represented by an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or an alkyl group having 2 to 20 carbon atoms Substituents of the heterocyclic group include ethylenically unsaturated groups such as vinyl, allyl, acryl, and methacrylate; halogen atoms such as fluorine, chlorine, bromine, and iodine; acetyl, 2-chloro Acetyl, propionyl, octyl, acryl, methacryloyl, phenylcarbonyl (benzyl), phthalyl, 4-trifluoromethylbenzyl, pivaloyl, o-hydroxybenzyl carboxyl, oxalyl, stearyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl, amine carboxyl, etc.; Ethyl Ethyloxy, benzyloxy and other acyloxy; amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexyl Amine, dodecylamine, aniline, chlorophenylamine, toluidine, methoxyaniline, N-methyl-anilino, diphenylamine, naphthylamino, 2-pyridine Amino, Methoxycarbonyl Amino, Phenoxycarbonyl Amino, Acetyl Amino, Benzyl Amino, Formyl Amino, Pivalamino Amino, Lauryl Amino, Aminocarboxylamino, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxy Carbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N , N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino and other substituted amino groups; , carboxyl group, cyano group, sulfo group, hydroxyl group, nitro group, mercapto group, imino group, amine carboxyl group, sulfonimide group, phosphonic acid group, phosphoric acid group or any of carboxyl, sulfo, phosphonic acid and phosphoric acid groups salt etc. As R 1 and R 2 , a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an aryl group having 6 to 12 carbon atoms are preferable because outgassing is small. When R 1 and R 2 are hydrogen atoms or branched alkyl groups having 1 to 8 carbon atoms, especially tertiary butyl groups, outgassing is less, which is more preferable. In the above general formula (IA), X 1 represents an n-valent bonding group, and specifically, for example, represents a direct bond, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, the following (Ia) or ( The group represented by Ib), -CO-, -NH-CO-, -CO-NH-, -NR 3- , -OR 3 , -SR 3 , -NR 3 R 4 , or having the same valence as n There are aliphatic hydrocarbon groups with 1 to 120 carbon atoms in the case of having a substituent, aromatic ring-containing hydrocarbon groups with 6 to 35 carbon atoms in the case of having a substituent, or 2 carbon atoms in the case of having a substituent ～35 heterocycle-containing groups, R 3 and R 4 represent hydrogen atoms, aliphatic hydrocarbon groups having 1 to 35 carbon atoms in the case of having a substituent, and those having 6 to 35 carbon atoms in the case of having a substituent Aromatic ring-containing hydrocarbon group or a heterocyclic ring-containing group having 2 to 35 carbon atoms in the case of having a substituent, aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic ring-containing group are substituted by carbon-carbon double bond , -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO- O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -O-CO-NH-, -NR'-, -SS-, -SO 2 - or in the case of radicals in nitrogen atoms. Wherein, when X 1 is a nitrogen atom, a phosphorus atom or a bonding group represented by the following (Ia) or (Ib), n is 3, and X 1 is an oxygen atom or a sulfur atom, -CO-, - In the case of NH-CO-, -CO-NH- or -NR 3- , n is 2, and when X 1 is a hydrogen atom, -OR 3 , -SR 3 or -NR 3 R 4 , n is 1 , X 1 may be integrated with the benzene ring to form a ring. [hua 3]
Figure 02_image009
(* means that the * part is bonded to an adjacent group.) The compound represented by the general formula (IA) has a structure in which n specific groups are bonded to the n-valent bonding group represented by X 1 . The n groups are the same or different from each other. The value of n is 1 to 10, and preferably 2 to 6 from the viewpoint of low outgassing. Examples of the aliphatic hydrocarbon group represented by X 1 in the above general formula (IA) and having the same valence as n, which may have a substituent, have a carbon number of 1 to 120, and examples where n is monovalent include, for example. : methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, cyclopentyl , hexyl, 2-hexyl, 3-hexyl, cyclohexyl, bicyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, third heptyl, n-octyl, Isooctyl, third octyl, 2-ethylhexyl, nonyl, isononyl, decyl and other alkyl groups; methoxy, ethoxy, propoxy, isopropoxy, butoxy, Dibutoxy, tert-butoxy, isobutoxy, pentyloxy, isopentyloxy, tert-pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, th Triheptyloxy, n-octyloxy, isooctyloxy, third octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy and other alkoxy groups; methylthio, ethylthio, propyl Thio, isopropylthio, butylthio, second butylthio, third butylthio, isobutylthio, pentylthio, isopentylthio, third pentylthio, hexylthio, cyclohexyl Thio, heptylthio, isoheptylthio, 3rd heptylthio, n-octylthio, isooctylthio, 3rd octylthio, 2-ethylhexylthio and other alkylthio groups; vinyl, 1 -Methylvinyl, 2-methylvinyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3- Alkenyl such as pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl, eicosenyl, eicosenyl ; And these groups are substituted by the substituents described later, etc.; As n is divalent, can enumerate: methylene, ethylidene, propylidene, butylene, butyldiyl and other alkylene groups; The methylene chain of the above-mentioned alkylene is substituted with -O-, -S-, -CO-O-, -O-CO-; ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol Residues of diols such as ethanedithiol, propanedithiol, butanedithiol, pentanedithiol, hexanedithiol and other dithiols; and these groups are substituted by the substituents described later groups, etc.; as n is trivalent, for example, alkylene groups such as propylene and 1,1,3-butylene groups; Examples of the aromatic ring-containing hydrocarbon group having the same valence as n and having a substituted group and having a carbon number of 6 to 35 include benzyl, phenethyl, and diphenylmethyl as n is monovalent. , triphenylmethyl, styryl, cinnamyl and other arylalkyl groups; phenyl, naphthyl and other aryl groups; phenoxy, naphthyloxy and other aryloxy groups; phenylthio, naphthylthio, etc. Arylthio groups; and groups in which these groups are substituted by substituents described later; as n is divalent, aryl groups such as phenylene, naphthylene, etc.; catechol, bisphenol, etc. Residues of functional phenols; 2,4,8,10-tetraoxaspiro[5,5]undecane; : Phenyl-1,3,5-trimethylene and groups in which these groups are substituted with the substituents described later. Examples of the heterocyclic group containing 2 to 35 carbon atoms having the same valence as n, which may have a substituent, and where n is monovalent include: pyridyl, pyrimidinyl, pyridyl, piperidine pyridyl, pyranyl, pyrazolyl, triazole, pyrrolyl, quinolinyl, isoquinolinyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl , benzofuranyl, thienyl, thiophenyl, benzothiophene, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl , indolyl, 2-pyrrolidin-1-yl, 2-piperidin-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidin- 3-yl, benzotriazolyl, etc.; and those substituted by substituents described later, etc.; as n is divalent, there may be mentioned: a pyridine ring, a pyrimidine ring, a piperidine ring, a piperidine ring, Groups such as tricyclic ring, furan ring, thiophene ring, indole ring, etc.; and groups in which these groups are substituted by substituents described later; As n is trivalent, there may be mentioned: groups having isocyanuric acid ring, A group having a tricyclic ring; and a group in which these groups are substituted with a substituent described later. Examples of the aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent represented by R 3 and R 4 include the aliphatic hydrocarbon group represented by the aforementioned X 1 and the combination of the aliphatic hydrocarbon group and the aforementioned substituent. Those that satisfy a specific number of carbon atoms are represented by R 3 and R 4 as an aromatic ring-containing hydrocarbon group with 6 to 35 carbon atoms in the case of having a substituent and a hydrocarbon group with 2 to 35 carbon atoms in the case of having a substituent. The heterocycle-containing group includes the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by X 1 and the heterocyclic ring-containing group having 2 to 35 carbon atoms, and combinations of these groups with the substituents described later. The formed base satisfies the specified number of carbon atoms. Examples of substituents include: ethylenically unsaturated groups such as vinyl, allyl, acrylic, and methacrylic groups; halogen atoms such as fluorine, chlorine, bromine, and iodine; acetyl, 2-chloroacetyl, Propionyl, octyl, acryloyl, methacryloyl, phenylcarbonyl (benzyl), phthaloyl, 4-trifluoromethylbenzyl, pivaloyl, o-hydroxybenzyl Acyl, oxalyl, stearyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl, amine carboxyl and other acyl groups; acetyloxy, Benzyl oxy and other oxy; amine, ethyl amine, dimethyl amine, diethyl amine, butyl amine, cyclopentyl amine, 2-ethylhexyl amine, ten Dialkylamine, aniline, chlorophenylamine, toluidine, methoxyaniline, N-methyl-aniline, diphenylamine, naphthylamine, 2-pyridylamine, Methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzylamino, methylamino, pivalamino, laurylamino, aminocarbamoyl Amine, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, The third butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N,N-di Substituted amine groups such as methylaminosulfonamido, methylsulfonamido, butylsulfonamido, phenylsulfonamido; sulfonamido, sulfonamido, carboxyl, cyano group, sulfo group, hydroxyl group, nitro group, mercapto group, imino group, carbamoyl group, sulfonamido group, phosphonic acid group, phosphoric acid group or carboxyl group, sulfo group, phosphonic acid group, salt of phosphoric acid group, etc. Isobases may then be substituted. In addition, a carboxyl group and a sulfo group may form a salt. In the above general formula (IA), when n is 2 to 6, X 1 may be represented by the following general formulae (1) to (5), respectively. [hua 4]
Figure 02_image011
(In the above general formula (1), Y 1 represents a single bond, -CR 5 R 6- , -NR 7- , a divalent aliphatic hydrocarbon group with 1 to 35 carbon atoms, and an aromatic group with 6 to 35 carbon atoms A hydrocarbon group or a group containing a heterocyclic ring having 2 to 35 carbon atoms, or any of the substituents represented by the following (1-1) to (1-3), the aliphatic hydrocarbon group is substituted with -O-, - S-, -CO-, -COO-, -OCO-, -NH-, -SO 2 -, -CONH- or -NHCO-, or a bond formed by combining these in such a way that the oxygen atoms are not adjacent In the case of a base, Z 1 and Z 2 independently represent a direct bond, -O-, -S-, >CO, -CO-O-, -O-CO-, -SO 2 -, -SS-, -SO -, -NR 7- or -PR 7- , R 5 , R 6 and R 7 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms in the case of having a substituent, and an aliphatic hydrocarbon group having a substituent In the case of an aromatic hydrocarbon group having 6 to 35 carbon atoms or a heterocyclic group containing 2 to 35 carbon atoms in the case of having a substituent, ﹡ means that the ﹡ part is bonded to an adjacent group) [Chem. 5 ]
Figure 02_image013
(In the above formula, R 8 represents a hydrogen atom, or a phenyl group having a substituent or a cycloalkyl group having 3 to 10 carbon atoms, and R 9 represents an alkyl group having 1 to 10 carbon atoms, a carbon number of 1 ~10 alkoxy groups, alkenyl groups with 2 to 10 carbon atoms or halogen atoms, the above alkyl groups, alkoxy groups and alkenyl groups may have substituents, f is an integer from 0 to 5, ﹡ means ﹡ part is bonded to the adjacent base) [化6]
Figure 02_image015
(﹡ means that the ﹡ part is bonded to the adjacent base) [Chem.7]
Figure 02_image017
(In the above formula, R 10 and R 11 each independently represent an alkyl group having 1 to 10 carbon atoms in the case of having a substituent, an aryl group having 6 to 20 carbon atoms in the case of having a substituent, and a group having In the case of a substituent, an aryloxy group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms in the case of having a substituent, and an arylthio group having 6 to 20 carbon atoms in the case of having a substituent Arylalkenyl group, arylalkyl group having 7 to 20 carbon atoms in the case of having a substituent, or a heterocyclic ring-containing group having 2 to 20 carbon atoms in the case of having a substituent, or a halogen atom, the alkyl group and the methylene group in the arylalkyl group may be substituted with an unsaturated bond, -O- or -S-, R 10 may form a ring by adjacent R 10 , p represents a number from 0 to 4, q represents a number from 0 to 8, g represents a number from 0 to 4, h represents a number from 0 to 4, the sum of the number of g and h is 2 to 4, ﹡ means that the ﹡ part is bonded to the adjacent base) [hua 8]
Figure 02_image019
(In the above general formula (2), Y 11 represents a trivalent aliphatic hydrocarbon group with 3 to 35 carbon atoms, an alicyclic hydrocarbon group with 3 to 35 carbon atoms, an aromatic hydrocarbon group with 6 to 35 carbon atoms, or a carbon A heterocyclic ring-containing group having 2 to 35 atoms, Z 1 , Z 2 and Z 3 each independently represent a direct bond, -O-, -S-, -CO-, -CO-O-, -O-CO- , -SO 2 -, -SS-, -SO-, -NR 12 - or -PR 12 -, R 12 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms in the case of having a substituent, or a In the case of a substituent, an aromatic hydrocarbon group having 6 to 35 carbon atoms or a heterocyclic ring-containing group having 2 to 35 carbon atoms in the case of having a substituent, an aliphatic hydrocarbon group substituted with a carbon-carbon double bond, - O-, -S-, -CO-, -COO-, -OCO-, -NH-, -SO2- , -CONH- or -NHCO-, or a combination of these in such a way that the oxygen atoms are not adjacent In the case of a bonded base, ﹡ means that the ﹡ part is bonded to the adjacent base) [Chem. 9]
Figure 02_image021
(In the above general formula (3), Y 12 represents a carbon atom, or a tetravalent aliphatic hydrocarbon group with 1 to 35 carbon atoms, an aromatic hydrocarbon group with 6 to 35 carbon atoms, or an impurity-containing hydrocarbon group with 2 to 35 carbon atoms. Ring base, the aliphatic hydrocarbon group is substituted with carbon-carbon double bond, -O-, -S-, -CO-, -COO-, -OCO-, -NH-, -SO 2 -, -CONH- Or -NHCO-, or in the case of a bonding group formed by combining these in such a way that the oxygen atoms are not adjacent, Z 1 to Z 4 are independently the same as Z 1 to Z 3 in the general formula (2) above. Represents the base of the same range as the base, ﹡ means that the part of ﹡ is bonded to the adjacent base) [化10]
Figure 02_image023
(In the above general formula (4), Y 13 represents a pentavalent aliphatic hydrocarbon group with 2 to 35 carbon atoms, an aromatic hydrocarbon group with 6 to 20 carbon atoms, or a group containing a heterocyclic ring with 2 to 20 carbon atoms, The aliphatic hydrocarbon group is substituted with a carbon-carbon double bond, -O-, -S-, -CO-, -COO-, -OCO-, -NH-, -SO 2 -, -CONH- or -NHCO- , or in the case of a bonding group formed by combining these in such a way that the oxygen atoms are not adjacent, Z 1 to Z 5 are independently the same as the groups represented by Z 1 to Z 3 in the general formula (2) above. The base of the range of , ﹡ means that the part of ﹡ is bonded to the adjacent base) [Chem. 11]
Figure 02_image025
(In the above general formula (5), Y 14 represents a hexavalent aliphatic hydrocarbon group with 2 to 35 carbon atoms, an aromatic hydrocarbon group with 6 to 35 carbon atoms, or a group containing a heterocyclic ring with 2 to 35 carbon atoms, The aliphatic hydrocarbon group is substituted with a carbon-carbon double bond, -O-, -S-, -CO-, -COO-, -OCO-, -NH-, -SO 2 -, -CONH- or -NHCO- , or in the case of a bonding group formed by combining these such that the oxygen atoms are not adjacent, Z 1 to Z 6 are independently the same as the groups represented by Z 1 to Z 3 in the general formula (2) above. The group within the range of ﹡ means that the part of ﹡ is bonded to the adjacent group.) In the above general formula (1), as R 5 , R 6 and R 7 represented by R 5 , R 6 and R 7 have the number of carbon atoms in the case of having a substituent The aliphatic hydrocarbon groups of 1 to 35 include monovalent aliphatic hydrocarbon groups exemplified as the n-valent bonding group represented by X 1 in the above general formula (IA), and these groups represented by the above general formula ( In IA), the substituent of the group of the n-valent bonding group represented by X 1 and the group substituted by the exemplified ones satisfies a specific number of carbon atoms, etc., as R 5 , R 6 and R 7 represented there are those with substitution Examples of the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms in the case of the group include monovalent aromatic ring-containing hydrocarbon groups exemplified as the n-valent bonding group represented by X 1 in the above general formula (IA), and the Such groups are exemplified as substituents of the group representing the n-valent bonding group represented by X 1 in the above general formula (IA), and the substituted group satisfies a specific number of carbon atoms, etc., as R 5 , R 6 . The heterocyclic ring-containing group having 2 to 35 carbon atoms, which may have a substituent represented by R 7 , may be exemplified as the n-valent bonding group represented by X 1 in the above general formula (IA). A monovalent heterocyclic ring-containing group, and those exemplified as a substituent representing an n-valent bonding group represented by X 1 in the above general formula (IA) satisfies a specific carbon in the group substituted atomic number etc. In addition, in the above general formula (1), as the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y 1 , the n-valent hydrocarbon group represented by X 1 in the above general formula (IA) can be exemplified. A divalent aliphatic hydrocarbon group exemplified as a bonding group, and a group in which these groups are substituted as a substituent of a group representing an n-valent bonding group represented by X 1 in the general formula (IA) above Those satisfying a specific number of carbon atoms, etc., as the divalent aromatic ring-containing hydrocarbon group represented by Y 1 having 6 to 35 carbon atoms, include: an n-valent bond represented by X 1 in the general formula (IA) above. The bivalent aromatic ring-containing hydrocarbon group exemplified as a bond group, and the group substituted by those exemplified as a substituent group representing the n-valent bond group represented by X 1 in the general formula (IA) above Those satisfying a specific number of carbon atoms, etc., as the divalent heterocyclic ring-containing group represented by Y 1 and having 2 to 35 carbon atoms, include the n-valent group represented by X 1 in the general formula (IA) above. Bivalent aromatic ring-containing hydrocarbon group exemplified as a bonding group, and a group in which these groups are substituted as a substituent of a group representing an n-valent bonding group represented by X 1 in the above general formula (IA) Among them, those satisfying a specific number of carbon atoms, etc. Among the substituents represented by the above (1-1), examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R 8 include cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, Cyclooctyl and the like, as the alkyl group having 1 to 10 carbon atoms represented by R 9 , among the groups exemplified as the alkyl group having 1 to 40 carbon atoms represented by R 1 and R 2 can be mentioned that satisfy specific carbon atoms. The number of atoms, etc., as the alkoxy group having 1 to 10 carbon atoms represented by R 9 include: methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, second butoxy group Oxy, tert-butoxy, isobutoxy, pentyloxy, isopentyloxy, tert-pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tert-heptyl oxy, n-octyloxy, isooctyloxy, tert-octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, etc., phenyl, cycloalkyl, alkyl, alkoxy and The substituent of the alkenyl group is the same as that exemplified as the substituent of the n-valent bonding group represented by X 1 in the above general formula (IA). Among the groups represented by the above (1-3), examples of the alkyl group having 1 to 10 carbon atoms which may have a substituent represented by R 10 and R 11 include those represented by R 1 and R 2 . Among the groups exemplified as alkyl groups having 1 to 40 carbon atoms, groups satisfying a specific number of carbon atoms, etc., aryl groups having 6 to 20 carbon atoms in the case of having a substituent represented by R 10 and R 11 , Examples include: groups exemplified as aryl groups having 6 to 20 carbon atoms represented by R 1 and R 2 ; groups having 6 to 20 carbon atoms that may have substituents represented by R 10 and R 11 Aryloxy groups include: phenoxy, naphthoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 4-vinylphenoxy, 3-methylphenoxy Isopropylphenoxy, 4-isopropylphenoxy, 4-butylphenoxy, 4-tert-butylphenoxy, 4-hexylphenoxy, 4-cyclohexylphenoxy, 4 -Octylphenoxy, 4-(2-ethylhexyl)phenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylbenzene oxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2,4-di-tert-butylphenoxy, 2 ,5-di-tert-butylphenoxy, 2,6-di-tert-butylphenoxy, 2,4-di-tert-pentylphenoxy, 2,5-tert-pentylphenoxy, Groups such as 4-cyclohexylphenoxy, 2,4,5-trimethylphenoxy, ferroceneoxy, etc. represented by R 10 and R 11 may have a carbon number of 6- The arylthio group of 20 includes a group in which the oxygen atom of the aryloxy group having 6 to 20 carbon atoms in the above-mentioned case having a substituent is substituted with a sulfur atom, etc., as represented by R 10 and R 11 . Examples of the arylalkenyl group having 8 to 20 carbon atoms in the case of having a substituent include replacing the oxygen atom of the aryloxy group having 6 to 20 carbon atoms in the case of having a substituent with a vinyl group, Allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl and other alkenyl groups, etc., as R 10 and The arylalkyl group having 7 to 20 carbon atoms which may have a substituent represented by R 11 may be exemplified as the arylalkyl group having 7 to 20 carbon atoms represented by R 1 and R 2 Groups, etc., as R 10 and R 11 , as the C 2-20 heterocyclic ring-containing group represented by R 10 and R 11, which may have a substituent, include: C 2-20 carbon atoms represented by R 1 and R 2 The group containing the heterocyclic ring and the group exemplified, etc. Examples of the trivalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y 11 in the above general formula (2) include: an n-valent bonding group represented by X 1 in the above general formula (IA) And the exemplified trivalent aliphatic hydrocarbon group and these groups are those that satisfy a specific number of carbon atoms among the exemplified groups substituted as a substituent of the n-valent bonding group represented by X 1 in the above general formula (IA), etc. Trivalent groups substituted by Z 1 , Z 2 and Z 3 , etc., as the trivalent alicyclic hydrocarbon group having 3 to 35 carbon atoms represented by Y 11 in the above general formula (2), include: Pentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, 1-adamantyl, 2-adamantyl, noradamantyl, 2-methyladamantyl, normantyl, isonoradamyl base, perhydronaphthyl, perhydroanthracenyl, bicyclo[1.1.0]butyl, bicyclo[1.1.1]pentyl, bicyclo[2.1.0]pentyl, bicyclo[3.1.0]hexyl, bicyclo[2.1 .1]hexyl, bicyclo[2.2.0]hexyl, bicyclo[4.1.0]heptyl, bicyclo[3.2.0]heptyl, bicyclo[3.1.1]heptyl, bicyclo[2.2.1]heptyl, bicyclo [5.1.0]octyl, bicyclo[4.2.0]octyl, bicyclo[4.1.1]octyl, bicyclo[3.3.0]octyl, bicyclo[3.2.1]octyl, bicyclo[2.2.2] Derived from octyl, spiro[4,4]nonyl, spiro[4,5]decyl, decalin, tricyclodecyl, tetracyclododecyl, cedaryl alcohol, cyclododecyl, etc. The trivalent group, etc., as the trivalent aromatic ring-containing hydrocarbon group represented by Y 11 and having 6 to 35 carbon atoms include: as the n-valent bonding group represented by X 1 in the above general formula (IA), The exemplified trivalent aromatic ring-containing hydrocarbon group and those exemplified as substituents of the n-valent bonding group represented by X 1 in the above general formula (IA) satisfy a specific number of carbon atoms in the exemplified groups substituted etc., as the trivalent C 2-35 heterocyclic ring-containing group represented by Y 11 , the third exemplified as the n-valent bonding group represented by X 1 in the above-mentioned general formula (IA) can be exemplified. The valent heterocyclic ring-containing group and the groups exemplified as substituents of the n-valent bonding group represented by X 1 in the above general formula (IA) satisfy a specific number of carbon atoms among the groups substituted. In addition, as R 12 , there are aliphatic hydrocarbon groups having 1 to 35 carbon atoms in the case of having a substituent, an aromatic hydrocarbon group having 6 to 35 carbon atoms in the case of having a substituent, and those having a substituent. The heterocycle - containing groups having 2 to 35 carbon atoms include the aliphatic hydrocarbon groups, aromatic ring - containing hydrocarbon groups, heterocyclic Ring base. In the above general formula (3), examples of the tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y 12 include an n-valent bond represented by X 1 in the above general formula (IA). A monovalent to trivalent aliphatic hydrocarbon group exemplified as a binding group and a group derived from a group substituted by those exemplified as a substituent of the n-valent bonding group represented by X 1 in the above general formula (IA) Among the tetravalent groups satisfying a specific number of carbon atoms, examples of the tetravalent aromatic ring-containing hydrocarbon group represented by Y 12 having 6 to 35 carbon atoms include those represented by X 1 in the general formula (IA) above. The n-valent bonding group represented by the univalent to trivalent aromatic ring-containing hydrocarbon group is exemplified, and these groups are exemplified as a substituent of the n-valent bonding group represented by X 1 in the above general formula (IA) Among the tetravalent groups derived from the substituted group that satisfy a specific number of carbon atoms, the tetravalent group represented by Y 12 and the heterocyclic ring-containing group having 2 to 35 carbon atoms can be exemplified by: As the n-valent bonding group represented by X 1 in (IA), monovalent to trivalent heterocyclic ring-containing groups and these groups are exemplified as the n-valent bond group represented by X 1 in the above general formula (IA) Among the tetravalent groups derived from the exemplified substituent of the bonding group, the tetravalent group satisfies a specific number of carbon atoms, and the like. Examples of the pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by Y 13 in the above general formula (4) include an n-valent bond represented by X 1 in the above general formula (IA). A monovalent to trivalent aliphatic hydrocarbon group is exemplified as a group, and these groups are derived from groups substituted by those exemplified as a substituent of the n-valent bonding group represented by X 1 in the general formula (IA) above. Among the valence groups, those satisfying a specific number of carbon atoms, etc., as the pentavalent aromatic ring-containing hydrocarbon group of 6 to 35 carbon atoms represented by Y 14 include: represented by X 1 in the above-mentioned general formula (IA) Monovalent to trivalent aromatic ring-containing hydrocarbon groups are exemplified as the n-valent bonding group, and these groups are substituted by those exemplified as substituents of the n-valent bonding group represented by X 1 in the above general formula (IA) Among the pentavalent groups derived from the group that satisfy a specific number of carbon atoms, the pentavalent group represented by Y 14 and the heterocyclic ring-containing group having 2 to 35 carbon atoms can be exemplified by: The n-valent bonding group represented by X 1 in ) is exemplified as a monovalent to trivalent heterocyclic ring-containing group and these groups are n-valent bonding represented by X 1 in the general formula (IA) above. Among the five-valent groups derived from the exemplified substituents as the substituents of the group satisfy the specified number of carbon atoms, and the like. Examples of the hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by Y 14 in the above general formula (5) include an n-valent bond represented by X 1 in the above general formula (IA). A monovalent to trivalent aliphatic hydrocarbon group is exemplified as a group, and these groups are derived from groups substituted by those exemplified as a substituent of the n-valent bonding group represented by X 1 in the general formula (IA) above. Among the valence groups satisfying a specific number of carbon atoms, examples of the hexavalent aromatic ring-containing hydrocarbon group represented by Y 14 having 6 to 35 carbon atoms include: represented by X 1 in the general formula (IA) above. Monovalent to trivalent aromatic ring-containing hydrocarbon groups are exemplified as the n-valent bonding group, and these groups are substituted by those exemplified as substituents of the n-valent bonding group represented by X 1 in the above general formula (IA) Among the hexavalent groups derived from the hexavalent group that satisfy a specific number of carbon atoms, the hexavalent group represented by Y 14 and the heterocyclic ring-containing group having 2 to 35 carbon atoms can be exemplified by the above general formula (IA The n-valent bonding group represented by X 1 in ) is exemplified as a monovalent to trivalent heterocyclic ring-containing group and these groups are n-valent bonding represented by X 1 in the general formula (IA) above. Among the hexavalent groups derived from the exemplified substituents of the group, the substituents satisfy a specific number of carbon atoms, and the like. Among the compounds represented by the above general formula (IA), those represented by the following general formulae (II-1) to (II-3) are preferred because their heat resistance is high. [Chemical 12]
Figure 02_image027
(in the formula, R 82 , R 83 and R 84 each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, or an alkyl group having 1 to 40 carbon atoms in the case of having a substituent, An aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a group containing a heterocyclic ring having 2 to 20 carbon atoms, R 1 and R 2 are the same as the general formula (I) above) [ 13]
Figure 02_image029
(in the formula, r=2～6, X 2 is the base represented by the above general formula (1) when r=2, the base represented by the above general formula (2) when r=3, and the base represented by the above general formula (2) when r=4 The group represented by the above-mentioned general formula (3) is the above-mentioned general formula (4) when r=5, and the above-mentioned general formula (5) when r=6, and R 92 and R 93 each independently represent a hydrogen atom, a halogen atom, A cyano group, a hydroxyl group, a nitro group, a carboxyl group, or an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms when it has a substituent, or Heterocycle-containing group having 2 to 20 carbon atoms, R 1 and R 2 are the same as those of the general formula (I) above) [Chemical 14]
Figure 02_image031
(wherein, R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , and R 208 each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, a substituted In the case of a group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a group containing a heterocyclic ring having 2 to 20 carbon atoms, Y 1. Z 1 and Z 2 are the same as in the general formula (1) above) as a halogen atom represented by R 82 , R 83 and R 84 in the above general formula (II-1), and a carbon atom in the case of having a substituent Alkyl groups with 1 to 40 carbon atoms, aryl groups with 6 to 20 carbon atoms, arylalkyl groups with 7 to 20 carbon atoms, and heterocycle-containing groups with 2 to 20 carbon atoms include the general formula (I ) in the description of R 1 and R 2 exemplified in the description. Examples of halogen atoms represented by R 92 and R 93 in the general formula (II-2), alkyl groups having 1 to 40 carbon atoms, aryl groups having 6 to 20 carbon atoms, carbon atoms The arylalkyl group having 7 to 20 atoms and the heterocyclic ring-containing group having 2 to 20 carbon atoms include those exemplified in the description of R 1 and R 2 in the above general formula (I). The halogen atom represented by R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , and R 208 in the general formula (II-3), and the number of carbon atoms in the case of having a substituent The alkyl group having 1 to 40 carbon atoms, the aryl group having 6 to 20 carbon atoms, the arylalkyl group having 7 to 20 carbon atoms, and the group containing a heterocyclic ring having 2 to 20 carbon atoms include the general formula (I) above. The one exemplified in the description of R 1 and R 2 . Among the compounds represented by the general formula (II-1), R 1 is preferably an alkyl group having a branched chain with 1 to 8 carbon atoms, especially a tertiary butyl group, and R 2 is a hydrogen atom; 82 , R 83 and R 84 are independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, and an arylalkyl group having 1 to 12 carbon atoms. The heterocycle-containing group of 10, especially any one of R 82 , R 83 and R 84 is an alkyl group having 1 to 4 carbon atoms or a heterocyclic ring-containing group having 1 to 10 carbon atoms. In the compound represented by the general formula (II-2), R 1 is preferably an alkyl group having a branched chain with 1 to 8 carbon atoms, especially a tertiary butyl group, and R 2 is a hydrogen atom; 92 and R 93 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, and a group containing 1 to 10 carbon atoms. A heterocyclic group, especially R 92 or R 93 is an alkyl group having 1 to 4 carbon atoms or a group containing a heterocyclic ring having 1 to 10 carbon atoms. When X 2 is the general formula (1), Y 10 is preferably a sulfur atom, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring-containing hydrocarbon group having 6 to 25 carbon atoms, 2-21 divalent heterocyclic group-containing group, divalent group derived from 2,4,8,10-tetraoxaspiro[5,5]undecane, especially preferably C 1-15 Alkyl, divalent aromatic ring-containing hydrocarbon group with 6 to 15 carbon atoms, divalent group derived from 2,4,8,10-tetraoxaspiro[5,5]undecane, Z 1 and Z 2 are more A direct bond, -CO-O-, -O-CO-, or an aliphatic hydrocarbon group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have substituents are preferable, and those which may have The substituent is an aliphatic hydrocarbon group having 1 to 8 carbon atoms. When X 2 is the general formula (2), Y 11 is preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkane having 7 to 12 carbon atoms. A trivalent group derived from a group or a group containing a heterocyclic ring having 1 to 10 carbon atoms, particularly preferably an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 9 carbon atoms, or an aryl group having 1 to 6 carbon atoms The trivalent group derived from the heterocycle-containing group, Z 1 , Z 2 and Z 3 are preferably the same as Z 1 and Z 2 , and when X 2 is in the above general formula (3), Y 12 is preferably The tetravalent groups corresponding to the groups listed above as preferred Y 11 , Z 1 to Z 4 are preferably the same as Z 1 and Z 2 , and when X 2 is the general formula (4), Y 13 is preferably a pentavalent base corresponding to the bases listed above as preferable Y 11 , Z 1 to Z 5 are preferably the same as Z 1 and Z 2 , and X 2 becomes the formula (5) above. In this case, Y 14 is preferably a hexavalent group corresponding to the groups listed above as preferable Y 11 , and Z 1 to Z 6 are preferably the same as Z 1 and Z 2 . Preferred among the compounds represented by the general formula (I) include the compounds represented by the following [Chemical 14] to [Formula 15], but the present invention is not limited to these compounds. [Chemical 15]
Figure 02_image033
[Chemical 16]
Figure 02_image035
The production method of the compound having the substituent represented by the above-mentioned general formula (I) is not particularly limited. Phenolic compounds, halogenated allyl compounds, etc. produced by the methods described in the gazettes of Japanese Patent Laid-Open No. 6-128195, Japanese Patent Laid-Open No. 7-206771, Japanese Patent Laid-Open No. 7-252191, and Japanese Patent Application Laid-Open No. 2004-501128 obtained by the reaction. The compound having the substituent represented by the general formula (I) can be used as a latent additive in the photosensitive composition of the present invention. The so-called latent additive mentioned above refers to being inert in the pre-baking step at room temperature, or below 150°C, for example, below 150°C, by heating at 100-250°C, or in the presence of an acid/alkali catalyst at 80-200°C. When heated at ℃, the protecting group is removed and becomes active. In the photosensitive composition of the present invention, the content of the compound having the substituent represented by the general formula (I) as a latent additive is preferably 0.001 to 20% by mass in the solid content of the composition of the present invention , more preferably 0.005 to 5 mass %. The photosensitive composition of the present invention is a composition whose properties are changed by light irradiation, and there is a positive-type resist which becomes soluble in chemical reaction, and a negative-type resist which becomes insoluble in chemical reaction. The photosensitive composition of the present invention also contains a polymerizable compound having an ethylenically unsaturated bond having an acid value and a photoradical in addition to the compound having the substituent represented by the general formula (I) as a latent antioxidant. A polymerization initiator is an essential ingredient. Examples of the polymerizable compound having an ethylenically unsaturated bond having an acid value include (meth)acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, methylmaleic acid, trans Butenedioic acid, bicycloheptenedicarboxylic acid, crotonic acid, methacrylic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, methyl fumaric acid, succinic acid mono[2-(methyl) ) Acryloyloxyethyl] ester, mono[2-(meth)acryloyloxyethyl] phthalate, ω-carboxypolycaprolactone mono(meth)acrylate are equal to having carboxyl groups at both ends Mono(meth)acrylate, hydroxyethyl(meth)acrylate-maleate, hydroxypropyl(meth)acrylate-maleate, dicyclopentane Unsaturated polybasic acids such as ene-maleate or polyfunctional (meth)acrylate having one carboxyl group and two or more (meth)acryloyl groups; phenol and/or cresol novolac epoxy Resins, novolak epoxy resins with biphenyl skeleton and naphthalene skeleton, bisphenol A novolac epoxy compounds, novolak epoxy compounds such as dicyclopentadiene novolak epoxy compounds, polyfunctional epoxy compounds Polyphenylmethane-based epoxy resins, epoxy compounds represented by the following general formula (III), etc. resins in which unsaturated monobasic acids act on epoxy groups of epoxy resins, and unsaturated monobasic acids act on epoxy resins The epoxy group of the resin and the resin obtained by further making the polybasic acid anhydride act on the epoxy group of the epoxy resin, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and other hydroxyl-containing polyfunctional acrylates and succinic anhydride, phthalate The reactants of dibasic acid anhydrides such as acid anhydride and tetrahydrophthalic anhydride are polyfunctional acrylates having an acid value, and the like. [Chemical 17]
Figure 02_image037
(in the formula, X 41 represents a direct bond, an alkylene group having 1 to 4 carbon atoms in the case of having a substituent, an alicyclic hydrocarbon group having 3 to 20 carbon atoms in the case of having a substituent, -O- , -S-, -SO 2 -, -SS-, -SO-, -CO-, -OCO- or the substituents represented by (1-1) to (1-3) above, R 41 , R 42 , R 43 and R 44 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms in the case of having a substituent, an alkoxy group having 1 to 8 carbon atoms in the case of having a substituent, or an alkoxy group having a substituent In the case of a group, an alkenyl group having 2 to 5 carbon atoms or a halogen atom, and m is an integer of 0 to 10.) These polymerizable compounds having an ethylenically unsaturated bond having an acid value can be used alone or in combination of two or more. Also, it can be used in combination with a polymerizable compound having an ethylenically unsaturated bond that does not have an acid value. When two or more types are mixed and used, it may be copolymerized in advance and used as a copolymer. In the photosensitive composition of the present invention, the content of the polymerizable compound having an ethylenically unsaturated bond having an acid value is preferably 20 to 80% by mass in the solid content of the composition of the present invention, and more preferably 30 to 70 mass % of the solid content. Examples of the polymerizable compound having an ethylenically unsaturated bond that does not have an acid value include (meth)acrylate-2-hydroxyethyl, (meth)acrylate-2-hydroxypropyl, (meth)acrylate Glycidyl acrylate, the following compounds No. A1 to No. A4, methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate , cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylate Lauryl acrylate, methoxyethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, aminopropyl (meth)acrylate , dimethylaminopropyl (meth)acrylate, ethoxyethyl (meth)acrylate, poly(ethoxy)ethyl (meth)acrylate, butoxyethoxy (meth)acrylate ethyl ester, ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofuran (meth)acrylate, vinyl (meth)acrylate, allyl (meth)acrylate, ( Benzyl meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate ) acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolethane triacrylate (Meth)acrylate, Trimethylolpropane tri(meth)acrylate, Dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, Pentaerythritol tetra(meth)acrylate, Pentaerythritol Tri(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, tris[(meth)acryloethyl]isocyanurate, polyester(meth)acrylate Esters of unsaturated monobasic acids and polybasic acids or polyphenols such as oligomers; metal salts of unsaturated polybasic acids such as zinc (meth)acrylate and magnesium (meth)acrylate; maleic anhydride, itaconic anhydride, methyl methacrylate maleic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuranyl)- 3-Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride, methylbicycloheptide Anhydrides of unsaturated polybasic acids such as enedicarboxylic anhydride; (meth)acrylamide, methylenebis-(meth)acrylamide, diethylenetriamine tri(meth)acrylamide, benzenediol Methyl bis(meth)acrylamide, α-chloroacrylamide, N-2-hydroxyethyl(meth)acrylamide and other unsaturated monobasic acids and polyamines; unsaturated aldehydes such as acrolein ; Unsaturated nitriles such as (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxy styrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, ethyl Unsaturated aromatic compounds such as alkenyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzyl methyl ether, vinylbenzyl glycidyl ether; methyl vinyl Unsaturated ketones such as ketone; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone, vinylpiperidine; vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl Ethyl vinyl ether, allyl glycidyl ether and other vinyl ethers; maleimide, N-phenylmaleimide, N-cyclohexylmaleimide and other unsaturated imide Amines; Indenes such as indene, 1-methylindene; 1,3-butadiene, isoprene, chloroprene and other aliphatic conjugated dienes; polystyrene, poly(meth)acrylic acid Methyl ester, poly(meth)acrylate n-butyl ester, polysiloxane are equal to macromonomers with mono(meth)acryloyl group at the end of the polymer molecular chain; (meth)acrylonitrile, ethylidene, Propylidene, butylene, vinyl chloride, vinyl acetate and other vinyl compounds, as well as polymethyl methacrylate macromonomers, polystyrene macromonomers and other macromonomers, and single tricyclodecane skeleton Copolymers of methacrylate, N-phenylmaleimide, methacryloyloxymethyl-3-ethyloxetane, etc. with (meth)acrylic acid, and the combination of these with (meth)acrylic acid For example, the copolymers of (meth)acrylic acid obtained by the reaction of isocyanate compounds with unsaturated bonds of Karenz MOI and AOI manufactured by Showa Denko Co., Ltd., or vinyl chloride, vinylidene chloride, divinyl succinate, ortho Diallyl Phthalate, Triallyl Phosphate, Triallyl Isocyanurate, Vinyl Sulfide, Vinylimidazole, Vinyloxazoline, Vinylcarbazole, Vinylpyrrolidone, Vinyl Pyridine, vinyl urethane compound of hydroxyl-containing vinyl monomer and polyisocyanate compound, vinyl epoxy compound of hydroxyl-containing vinyl monomer and polyepoxy compound, pentaerythritol triacrylate, dipentaerythritol penta Reaction products of polyfunctional acrylates containing hydroxyl groups such as acrylates and polyfunctional isocyanates such as toluene diisocyanate and hexamethylene diisocyanate, etc. [Chemical 18]
Figure 02_image039
[Chemical 19]
Figure 02_image041
[hua 20]
Figure 02_image043
[Chemical 21]
Figure 02_image045
In order to adjust the acid value and improve the developability of the photosensitive composition of the present invention, a monofunctional or polyfunctional epoxy compound can be used together with the polymerizable compound having an ethylenically unsaturated bond having an acid value. The above-mentioned polymerizable compound having an acid value with an ethylenically unsaturated bond is preferably in the range of the acid value of the solid content of 5 to 120 mgKOH/g, and the amount of the monofunctional or polyfunctional epoxy compound used is preferably to satisfy the The above acid value is selected. Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isopropyl glycidyl ether, and Butyl glycidyl ether, tert-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, ten Monoalkyl glycidyl ether, lauryl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethyl acetate Hexyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether Ether, tolyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumyl phenyl glycidyl ether, trityl glycidyl ether Glyceryl ether, 2,3-glycidyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, ethylene cyclohexane, 1,2-epoxy-4- Vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, epoxycyclohexane, propylene oxide, etc. As the polyfunctional epoxy compound, it is preferable to use at least one selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers, since a photosensitive composition with better properties can be obtained. As the bisphenol-type epoxy compound, in addition to the epoxy compound represented by the above-mentioned general formula (III), for example, a bisphenol-type epoxy compound such as a hydrogenated bisphenol-type epoxy compound can also be used. As the glycidyl ethers, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 8-Octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triglyceride Ethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tris(glycidyl ether) oxymethyl)propane, 1,1,1-tris(glycidoxymethyl)ethane, 1,1,1-tris(glycidoxymethyl)methane, 1,1,1,1- Tetrakis(glycidoxymethyl)methane. In addition, phenol novolak type epoxy compounds, biphenyl novolak type epoxy compounds, cresol novolak type epoxy compounds, bisphenol A novolak type epoxy compounds, dicyclopentadiene novolak type epoxy compounds, and dicyclopentadiene novolak type epoxy compounds can also be used. Novolak-type epoxy compounds such as oxygen compounds; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4- Alicyclic epoxy compounds such as epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane; phthalic acid diglycidate Glycidyl esters such as glycerol ester, diglycidyl tetrahydrophthalate, glycidyl dimer acid, etc.; tetraglycidyl diaminodiphenylmethane, triglycidyl p-aminophenol, N,N - Glycidyl amines such as diglycidyl aniline; 1,3-diglycidyl-5,5-dimethylhydantoin, triglycidyl isocyanurate and other heterocyclic epoxy compounds; dioxide Dioxide compounds such as dicyclopentadiene; naphthalene-type epoxy compounds, triphenylmethane-type epoxy compounds, dicyclopentadiene-type epoxy compounds, etc. The above-mentioned photoradical polymerization initiator may be a compound capable of initiating radical polymerization by being irradiated with light, and examples thereof include acetophenone-based compounds, benzophenone-based compounds, benzophenone-based compounds, 9 -oxysulfur 𠮿
Figure 106110457-xxxx-3
Preferred are ketone-based compounds such as ketone-based compounds, oxime-based compounds, and the like. Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2 -Methyl propiophenone, 2-hydroxymethyl-2-methyl propiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminophenethyl Ketone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzylidene acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1 -[4-(Methylthio)phenyl]-2-morpholinylacetone-1,2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone- 1. Benzoin, Benzoin methyl ether, Benzoin ether, Benzoin isopropyl ether, Benzoin n-butyl ether, Benzoin isobutyl ether, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2- Methyl-1-propan-1-one, etc. As a benzil compound, a benzil, anisole, etc. are mentioned. Examples of the benzophenone-based compound include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4'-dichlorobenzophenone, 4-benzyl-4'-methyl diphenyl sulfide, etc. as 9-oxysulfur 𠮿
Figure 106110457-xxxx-3
series of compounds, such as: 9-oxosulfur 𠮿
Figure 106110457-xxxx-3
, 2-methylthio ketone, 2-ethyl-9-oxothio
Figure 106110457-xxxx-3
, 2-chloro-9-oxysulfur
Figure 106110457-xxxx-3
, 2-isopropylthio ketone, 2,4-diethyl-9-oxosulfan
Figure 106110457-xxxx-3
Wait. As the oxime-based compound, a compound represented by the following general formula (IV) or (V) is particularly preferable in terms of sensitivity and heat resistance. [Chemical 22]
Figure 02_image047
(In the formula, R 51 and R 52 each independently represent a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms in the case of having a substituent, and an alkyl group having 6 to 30 carbon atoms in the case of having a substituent Aryl group, arylalkyl group having 7 to 30 carbon atoms in the case of having a substituent, or a group containing a heterocyclic ring having 2 to 20 carbon atoms in the case of having a substituent, R 53 and R 54 are each independently Indicates halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, R 55 , OR 56 , SR 57 , NR 58 R 59 , COR 60 , SOR 61 , SO 2 R 62 or CONR 63 R 64 , R 53 and R 54 have When a ring is formed by bonding with each other, R 55 , R 56 , R 57 , R 58 , R 59 , R 60 , R 61 , R 62 , R 63 and R 64 each independently represent a carbon having a substituent. An alkyl group having 1 to 20 atoms, an aryl group having a substituent group having 6 to 30 carbon atoms, an arylalkyl group having a substituent group having a carbon number of 7 to 30, or an aryl group having a substituent group In the case of a heterocyclic ring-containing group having 2 to 20 carbon atoms, X 3 represents an oxygen atom, a sulfur atom, a selenium atom, CR 75 R 76 , CO, NR 77 or PR 78 , X 4 represents a single bond or CO, and R 75 ~R 78 represents an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms or an arylalkyl group with 7 to 30 carbon atoms, and the methylene group in the alkyl group or arylalkyl group is either There are cases where it is substituted with halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group or a group containing a heterocyclic ring, and there is a case where it is substituted with -O-, R 53 and R 54 are independently any adjacent benzene When the rings are integrated to form a ring, a represents an integer from 0 to 4, and b represents an integer from 0 to 5) [Chem. 23]
Figure 02_image049
(wherein, R 101 and R 102 each independently represent R 111 , OR 111 , COR 111 , SR 111 , CONR 112 R 113 or CN, and R 111 , R 112 and R 113 each independently represent a hydrogen atom and the number of carbon atoms 1-20 alkyl group, 6-30 carbon atom aryl group, 7-30 carbon atom arylalkyl group or 2-20 carbon atom-containing heterocyclic group, R 111 , R 112 and R 113 The hydrogen atom of the represented group has further through R 121 , OR 121 , COR 121 , SR 121 , NR 122 R 123 , CONR 122 R 123 , -NR 122 -OR 123 , -NCOR 122 -OCOR 123 , NR 122 COR 121 , OCOR 121 , COOR 121 , SCOR 121 , OCSR 121 , COSR 121 , CSOR 121 , substituted by hydroxyl, nitro, CN or halogen atoms, R 121 , R 122 and R 123 independently represent hydrogen atoms and carbon atoms, respectively An alkyl group of 1-20, an aryl group of 6-30 carbon atoms, an arylalkyl group of 7-30 carbon atoms or a group containing a heterocyclic ring of 2-20 carbon atoms, R 121 , R 122 and R 123 The hydrogen atom of the represented group may be further substituted by a hydroxyl group, a nitro group, CN , a halogen atom , a hydroxyl group or a carboxyl group. The alkyl part is substituted 1-5 times under the condition that the oxygen atoms are not adjacent to -O-, -S-, -COO-, -OCO-, -NR 124- , -NR 124 COO-, -OCONR 124 - , -SCO-, -COS-, -OCS- or -CSO-, R 124 represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, and a carbon number of 7 Arylalkyl group of to 30 or group containing a heterocyclic ring of carbon number of 2 to 20, the alkyl part of the group represented by R 111 , R 112 , R 113 , R 121 , R 122 , R 123 and R 124 is both There are cases of branched side chains, and there are cases of cyclic alkyl groups. R 103 represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, and a group with 7 to 30 carbon atoms. The arylalkyl group or the group containing a heterocyclic ring with 2 to 20 carbon atoms, the alkyl part of the group represented by R 103 has both a branched side chain and a cyclic alkyl group, and, R 103 and R 107 , R 103 and R 108 , R 104 and R 105 , R 105 and R 106 , and R 106 and R 107 are respectively integrated to form a ring In this case, the hydrogen atom of the group represented by R 103 has further undergone R 121 , OR 121 , COR 121 , SR 121 , NR 122 R 123 , CONR 122 R 123 , -NR 122 -OR 123 , -NCOR 122 -OCOR 123 , NR 122 COR 121 , OCOR 121 , COOR 121 , SCOR 121 , OCSR 121 , COSR 121 , CSOR 121 , hydroxyl, nitro, CN, halogen, or COOR 121 substitution, R 104 , R 105 , R 106 and R 107 independently represents R 111 , OR 111 , SR 111 , COR 114 , CONR 151 R 116 , NR 112 COR 111 , OCOR 111 , COOR 114 , SCOR 111 , OCSR 111 , COSR 114 , CSOR 111 , hydroxyl, CN or halogen Atom, R 104 and R 105 , R 105 and R 106 , and R 106 and R 107 may be integrated to form a ring, respectively, and R 114 , R 115 and R 116 represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. , R 108 represents R 111 , OR 111 , SR 111 , COR 111 , CONR 112 R 113 , NR 112 COR 111 , OCOR 111 , COOR 111 , SCOR 111 , OCSR 111 , COSR 111 , CSOR 111 , hydroxyl, CN or halogen atom , w represents 0 or 1) As other photo-radical polymerization initiators, 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(cyclopentadienyl)-bis[ 2,6-difluoro-3-(pyl-1-yl)] titanium, etc. These photo-radical polymerization initiators may be used in combination of one or two or more types in accordance with desired properties. 0.1-30 mass % is preferable in the solid content of the photosensitive composition of this invention, and, as for content of the above photoradical polymerization initiator, 0.5-10 mass % is especially preferable. If content of the said photoradical polymerization initiator is less than 0.1 mass %, hardening by exposure may become inadequate, and if it exceeds 30 mass %, an initiator may precipitate in a photosensitive composition. The photosensitive composition of this invention can also add a coloring agent further, and can set it as a coloring photosensitive composition. The hardened|cured material of this coloring photosensitive composition can be used suitably as a color filter. In the coloring photosensitive composition of the present invention, the amount of the colorant added is preferably 0.01 to 50% by mass, more preferably 0.1 to 30% by mass in the solid content of the coloring photosensitive composition of the present invention. When content of the said coloring agent is less than 0.01 mass %, a desired chromaticity may not be obtained, and when it exceeds 50 mass %, a coloring agent may precipitate in a colored photosensitive composition. As said coloring agent, a dye or a pigment is mentioned. The dye is not particularly limited as long as it is a compound having absorption at 380 to 1200 nm, and examples thereof include azo compounds, anthraquinone compounds, indigo compounds, triarylmethane compounds,
Figure 106110457-xxxx-3
compounds, alizarin compounds, acridine compounds, stilbene compounds, thiazole compounds, naphthol compounds, quinoline compounds, nitro compounds, indamide compounds, cyanine compounds, phthalocyanine compounds, cyanine compounds, diimmonium compounds, Cyanovinyl compound, dicyanostyrene compound, rose bengal compound, perylene compound, polyene naphthalamide compound, coumarin compound, squaraine compound, ketone compound, spiropyran compound, spiro 𠯤 compounds, merocyanine compounds, oxo compounds, styryl compounds, pyrylium compounds, rhodanine compounds, oxazolinone compounds, phthalimide compounds, phytoline compounds, naphthoquinone compounds, Azaanthraquinone compounds, porphyrin compounds, azaporphyrin compounds, pyrrole methylene compounds, quinacridone compounds, diketopyrrolopyrrole compounds, indigo compounds, acridine compounds, acridine compounds, methimine compounds , dyes such as aniline compounds, quinacridone compounds, quinophthalone compounds, quinoneimine compounds, iridium complex compounds, europium complex compounds, etc., and these may be mixed and used in plural. As pigments, inorganic pigments or organic pigments can be used, for example, nitroso compounds, nitro compounds, azo compounds, disazo compounds,
Figure 106110457-xxxx-3
Compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridone compounds, anthraquinone compounds, perrenone compounds, perylene Compounds, diketopyrrolopyrrole compounds, thioindigo compounds, bismuth compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acids; metal complex compounds of azo dyes, cyanine dyes; lakes Pigment; obtained by adjusting and coating the above carbon black with epoxy resin, obtained by dispersing the above carbon black in a solvent in advance with a resin and absorbing 20-200 mg/g of the resin, acidifying the above carbon black Or those obtained by alkaline surface treatment, with an average particle size of 8 nm or more and a DBP oil absorption of 90 ml/100 g or less, the total oxygen content calculated from CO and CO 2 in the volatile components at 950°C relative to carbon Black is 9 mg or more per surface area of 100 m2; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, helical carbon fiber, carbon nanohorn, carbon aerogel, fullerene; aniline black, Pigment Black 7, Titanium Black; Hydrophobic Resin, Chromium Oxide Green, Milori Blue, Cobalt Green, Cobalt Blue, Manganese, Ferrocyanide, Phosphate Ultramarine, Iron Blue, Ultramarine, Sky Blue, Dark Green, Emerald Green , lead sulfate, lead yellow, zinc yellow, iron red (iron oxide red (III)), cadmium red, synthetic iron black, umber and other inorganic content or organic pigments. These pigments may be used alone or in combination. As the inorganic pigment or organic pigment, commercially available pigments can also be used, for example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc. A solvent can be further added to the photosensitive composition and coloring photosensitive composition of this invention. Examples of the solvent include solvents that can dissolve or disperse the above-mentioned components as necessary, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, Ketones such as methyl isobutyl ketone, cyclohexanone, 2-heptanone; ether, diethyl, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethyl ether Ether solvents such as propylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, TEXANOL and other esters solvents; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol, and diacetone alcohol; Glycol Monomethyl Acetate, Ethylene Glycol Monoethyl Acetate, Propylene Glycol-1-Monomethyl Ether-2-Acetate (PGMEA), Dipropylene Glycol Monomethyl Ether Acetate, 3-Methoxy Acetate Ether ester solvents such as butyl butyl, ethoxyethyl propionate, 1-tert-butoxy-2-propanol, 3-methoxybutyl acetate, cyclohexanol acetate; benzene, toluene, BTX-based solvents such as xylene; aliphatic hydrocarbon-based solvents such as hexane, heptane, octane, and cyclohexane; terpene-based hydrocarbon oils such as turpentine, D-limonene, and pinene; mineral spirits, Swazol #310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso #100 (Exxon Chemical Co., Ltd.) and other paraffin-based solvents; carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane and other halogenated aliphatic solvents Hydrocarbon-based solvents; halogenated aromatic hydrocarbon-based solvents such as chlorobenzene; carbitol-based solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N- Dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, water, etc., these solvents can be used as one or more mixed solvents. Among them, ketones, ether ester-based solvents, etc., especially propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, etc. are photosensitive compositions, and the resist and photoradical polymerization are started The compatibility of the agent is good, so it is preferred. When using a solvent, it is preferable to use it in the quantity which becomes 25-35 mass % of the solid content of the photosensitive composition of this invention or a coloring photosensitive composition from viewpoints, such as handleability. An inorganic compound may be further contained in the photosensitive composition and coloring photosensitive composition of this invention. Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silicon dioxide, and aluminum oxide; layered clay minerals, rice Loli blue, calcium carbonate, magnesium carbonate, cobalt series, manganese series, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfide, selenide, aluminum silicate, calcium silicate, hydrogen Alumina, platinum, gold, silver, copper, etc. In the case of using a colorant such as a pigment and/or an inorganic compound in the photosensitive composition and the colored photosensitive composition of the present invention, a dispersant may be added. The dispersing agent is not particularly limited as long as it can disperse and stabilize colorants and inorganic compounds, and commercially available dispersing agents, such as BYK series manufactured by BYK-Chemie, can be suitably used. Basic functional group polyester, polyether, polyurethane polymer dispersant, with nitrogen atom as basic functional group and the functional group with nitrogen atom is amine and/or its quaternary salt and amine value 1 to 100 mgKOH/g. In addition, to the photosensitive composition and the colored photosensitive composition of the present invention, heat such as p-anisole, hydroquinone, catechol, tert-butyl catechol, and phenothiazine may be added as needed. Polymerization inhibitors; Plasticizers; Adhesion accelerators; Fillers; Agents; dispersing aids; agglomeration inhibitors; catalysts; effect accelerators; cross-linking agents; tackifiers and other commonly used additives. Moreover, the characteristic of the hardened|cured material of the photosensitive composition of this invention and a coloring photosensitive composition can also be improved by using together the polymerizable compound which has an ethylenically unsaturated bond which has an acid value, and another organic polymer. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, and styrene-(meth)acrylic acid copolymer. , (meth)acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane Ester resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, phenoxy resin, polyamide imide resin, polyamide acid resin, epoxy resin, etc. , Among them, polystyrene, (meth)acrylic acid-methyl methacrylate copolymer, and epoxy resin are also preferred. In the photosensitive composition and the colored photosensitive composition of the present invention, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine compound, etc. can be used in combination. As the above-mentioned chain transfer agent and sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine acid, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)aminocarbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-( 3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, mercapto compounds such as 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), etc. Disulfide compounds obtained by oxidizing mercapto compounds, iodized alkyl compounds such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, and 3-iodopropanesulfonic acid, trimethylolpropane trimethylolide (3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bis-mercaptopropane Acetate, Butylene Glycol Dithioglycolate, Ethylene Glycol Dithioglycolate, Trimethylolpropane Trimercaptoacetate, Butylene Glycol Dimercaptopropionate, Trimethylolpropane Trimercaptopropionic Acid Esters, Trimethylolpropane Trimercaptoacetate, Pentaerythritol Tetramercaptopropionate, Pentaerythritol Tetramercaptopropionate, Trishydroxyethyl Trimercaptopropionate, The following Compound No.C1, Trimercaptopropionate Tris( Aliphatic polyfunctional thiol compounds such as 2-hydroxyethyl) isocyanurate, Karenz MT BD1, PE1, NR1, etc. manufactured by Showa Denko Corporation. [Chemical 24]
Figure 02_image051
As the above-mentioned surfactants, fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, and anionic surfactants such as higher fatty acid alkali metal salts, alkyl sulfonates, and alkyl sulfates can be used. cationic surfactants such as higher amine hydrohalide salts, quaternary ammonium salts, etc., nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides, etc. Surfactants such as surfactants, amphoteric surfactants, and polysiloxane-based surfactants can also be used in combination. As the above-mentioned silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Among them, KBE-9007, KBM-502, KBE-403, etc. having an isocyanate group, a methacryloyl group, and an epoxy group are preferably used. Silane coupling agent. Examples of the melamine compound include active methylol groups in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. A compound in which all or a part (at least 2) of (CH 2 OH group) is etherified with an alkyl group. Here, a methyl group, an ethyl group, or a butyl group may be mentioned as an alkyl group which comprises an alkyl ether, and may be the same as each other, and may be different. In addition, the methylol group which is not alkyl-etherified may undergo self-condensation in one molecule, and may also be condensed between two molecules, and as a result, an oligomer component may be formed. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril, etc. can be used. Among these, alkyl-etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferred. The photosensitive composition and the colored photosensitive composition of the present invention can be applied by a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various types of printing, dipping Such well-known means are applied to support substrates such as soda glass, quartz glass, semiconductor substrates, metals, paper, and plastics. In addition, it can also be transferred to another support substrate after being temporarily applied to a support substrate such as a film, and the application method thereof is not limited. In addition, as a light source of active light used for curing the photosensitive composition and the colored photosensitive composition of the present invention, one that emits light with a wavelength of 300 to 450 nm can be used, for example, ultra-high pressure mercury, mercury vapor arc, Carbon arc, xenon arc, etc. Furthermore, the laser direct drawing method in which an image is directly formed from digital information such as a computer without using a mask using laser light as an exposure light source not only improves productivity, but also improves resolution, positional accuracy, and the like. , so it is more useful. As the laser light, it is suitable to use light with a wavelength of 340 to 430 nm, and also use argon ion lasers, helium-neon lasers, YAG lasers, and semiconductor lasers that emit light in the visible to infrared region. . In the case of using these lasers, a sensitizing dye in the region that absorbs visible light to infrared is added. The photosensitive composition and the colored photosensitive composition of the present invention can also be patterned through a double patterning process in which two kinds of photosensitive compositions or colored photosensitive compositions are patterned in two steps. The method of hardening the photosensitive composition or the colored photosensitive composition of the present invention includes the steps of: using the above-mentioned spin coater, roll coater, bar coater, die coater, curtain coater Coater, various printing, dipping and other well-known means, coating on soda glass, quartz glass, semiconductor substrate, metal, paper, plastic and other supporting substrates to form a coating film; and exposing the coating film to the above-mentioned active light to make it hardening. The photosensitive composition and colored photosensitive composition (or its cured product) of the present invention can be used for photocurable paints or varnishes, adhesives such as photocurable adhesives, printed circuit boards, or color TVs, PC monitors, portable type Color filters for liquid crystal display panels for color displays such as information terminals and digital cameras, color filters for CCD image sensors, photosensitive spacers, black column spacers, electrode materials for plasma display panels, touch Panels, touch sensors, powder coatings, printing inks, printing plates, dental compositions, resins for photomodeling, gel coats, photoresists for electronic engineering, electroplating resists, etching resists, Both liquid and dry films, solder resists, resists for the manufacture of color filters for various display applications or for structure formation in the manufacturing steps of plasma display panels, electroluminescence display devices and LCDs, Compositions for encapsulating electrical and electronic parts, solder resists, magnetic recording materials, micromechanical parts, waveguides, optical switches, masks for plating, etching masks, color test systems, glass fiber cable coatings, stencils Templates for printing, materials for producing three-dimensional objects by stereolithography, materials for holographic recording, image recording materials, microelectronic circuits, decolorizing materials, decolorizing materials for image recording materials, using microcapsules Decolorizing materials for image recording materials, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct image systems, photoresists for forming dielectric layers in successive lamination of printed circuit boards Various uses such as materials, photoresist materials for 3D mounting, and protective films are not particularly limited. The photosensitive composition of this invention can be used as a transparent structure by hardening. Examples of the transparent structure include: pillars called photo spacers (PS) and column spacers (CS); (nano) imprinted fine patterns; large-scale billboards, etc.; manufacture of liquid crystals Inkjet receiving layers used in the manufacture of electronic devices such as color filters for displays or printing of alignment films, etc. The transparent structure of the present invention is suitable for use in a display device. The photosensitive composition of the present invention can be used for transparent conductive films, reflective films, polarizers, protective films, etc., and can be used as transparent laminates laminated by the following method, that is, by sequentially coating desired layers on a transparent substrate, The active light is irradiated through a mask having a specific pattern shape, the exposed film is developed with a developer, and the developed film is heated. As a transparent laminated body, the thing in which the transparent thin film layer and the metal thin film layer containing the composite oxide of indium oxide and cerium oxide were alternately formed on a transparent base material, etc. are mentioned, for example. The photosensitive composition of this invention containing the compound which has the substituent represented by general formula (I) as a latent additive can be used for each of the said each layer, and this photosensitive composition can also be used for any layer. Furthermore, this transparent laminate is suitable for use in a display device. The colored photosensitive composition of the present invention is used for the purpose of forming a pixel of a color filter, and is particularly useful as a photosensitive composition for forming a color filter for display devices for image display devices such as liquid crystal display panels . The above-mentioned color filter for a display device is preferably formed by the following steps: (1) forming a coating film of the colored photosensitive composition of the present invention on a substrate; (2) through a mask having a specific pattern shape The coating film is irradiated with active light; (3) the exposed coating film is developed with a developer; (4) the coating film after the development is heated. Moreover, the coloring photosensitive composition of this invention is useful also as a coloring photosensitive composition of the inkjet method without a development process. As the above-mentioned mask, a multi-step mask such as a halftone mask or a grayscale mask can also be used. Next, the novel compound of the present invention will be described. The novel compounds of the present invention are represented by any of the following structures. [Chemical 25]
Figure 02_image053
[Chemical 26]
Figure 02_image055
[Chemical 27]
Figure 02_image057
The production method of the novel compound of the present invention is not particularly limited. It is obtained by reacting the phenolic compound produced by the method described in each publication of Japanese Patent Laid-Open No. 7-206771, Japanese Patent Laid-Open No. 7-252191, and Japanese Patent Publication No. 2004-501128 with a halogenated allyl compound or the like. The novel compounds of the present invention can be used as latent antioxidants, latent ultraviolet absorbers, dissolution modifiers, and the like. [Examples] Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the present invention is not limited to these Examples and the like. [Example 1-1] Synthesis of Compound No. 1 Potassium carbonate (relative to 1 2 equivalents of phenolic groups), and stirred at room temperature for 30 minutes. Allyl bromide (1.5 equivalent with respect to 1 phenol group) was added, and it stirred at 60 degreeC for 5 hours. Ethyl acetate was added, washed with a 1% hydrochloric acid solution, and then oil-water separation was carried out. After drying the organic layer with anhydrous sodium sulfate, the solvent was distilled off to carry out crystallization. The obtained solid was dried under reduced pressure at 60°C for 3 hours to obtain the target product. The obtained solid was confirmed to be the target object by 1 H-NMR and IR. The results are shown in [Table 1] to [Table 2]. [Examples 1-2 to 1-6] Synthesis of Compound Nos. 2 to 6 In Example 1-1, the phenolic compounds of the following Compound No. 2' to 6' were used instead of the following Compound No. 1' Except for the phenol compound, compounds Nos. 2 to 6, which are the target objects, were synthesized in the same manner as in Example 1-1. The obtained solid was confirmed to be the target object by 1 H-NMR and IR. The results are shown in [Table 1] to [Table 2]. [Chemical 28]
Figure 02_image059
[Chemical 29]
Figure 02_image061
[Table 1]
Figure 106110457-A0304-0001
 [Table 2]
Figure 106110457-A0304-0002
 [Examples 2-1 to 2-2 and Comparative Examples 2-1 to 2-3] Preparation of photosensitive compositions No. 1 to No. 2 and comparative photosensitive compositions No. 1 to No. 3 SPC- 1000 (manufactured by Showa Denko Co., Ltd., PGMEA solution with a solid content of 29%) 50.0 g, ARONIX M-450 (manufactured by Toagosei Co., Ltd.) 11.6 g, NCI-930 (manufactured by ADEKA Co., Ltd.) 0.3 g, PGMEA34.7 g, FZ2122 ( Dow Corning Toray Co., Ltd., 2.9 g of a PGMEA solution with a solid content of 1%) and 0.81 g of the compound described in [Table 3] were mixed, and stirred until the insoluble matter disappeared to obtain photosensitive compositions No. 1 to No. 2 and The photosensitive compositions No. 1 to No. 3 were compared. [table 3]
Figure 106110457-A0304-0003
 [Chemical 30]
Figure 02_image063
[Chemical 31]
Figure 02_image065
[Chemical 32]
Figure 02_image067
[Evaluation Example 1-1 and Comparative Evaluation Example 1-1] Outgassing Evaluation Compound No. 1, Compound No. 2, and Comparative Compound No. 2 were weighed in 5 mg, respectively, and the temperature was increased from room temperature (20° C.) using a thermal mass measurement device. /min.) to 230°C, the weight reduction rate at the time point of holding at 230°C for 30 minutes was measured as the outgassing evaluation of the photosensitive compositions No. 1 to No. 2 and the comparative photosensitive composition No. 2 . Smaller weight reductions indicate less outgassing. The results are shown in [Table 4]. [Table 4]
Figure 106110457-A0304-0004
 From the above results, it was found that the outgassing of the compound of the present invention was small, and the outgassing of the photosensitive composition of the present invention containing the compound of the present invention was reduced. [Evaluation Example 2-1 and Comparative Evaluation Examples 2-1 to 2-2] Solvent Resistance Evaluation The photosensitive composition No. 1 and Comparative Examples 2-1 and 2-3 obtained in the above-mentioned Example 2-1 were used The comparative photosensitive compositions No. 1 and No. 3 obtained in each were applied to a glass substrate under the conditions of 410 rpm×7 seconds, respectively, and dried with a hot plate (90° C.×90 seconds). The obtained coating film was exposed to light (40 mJ/cm 2 ) using an ultra-high pressure mercury lamp. The exposed coating film was fired under the conditions of 230° C.×30 minutes. After measuring the film thickness of the obtained coating film, it was immersed in PGMEA, cyclohexanone, N-methylpyrrolidone, and N-ethylpyrrolidone at room temperature for 30 minutes, and the film thickness after immersion was measured. The film thickness ratio before and after immersion (film thickness after immersion×100/film thickness before immersion) was closer to 100%, and the solvent resistance evaluation was higher. [table 5]
Figure 106110457-A0304-0005
 As can be seen from [Table 5], the solvent resistance of the cured product of the comparative photosensitive composition No. 1 containing the conventional phenolic antioxidant is compared with the cured product of the comparative photosensitive composition No. 3 that does not contain an antioxidant. However, the photosensitive composition No. 1 using the compound of the present invention as a latent additive maintained the same solvent resistance as the case without antioxidant. From the above results, it was found that the photosensitive composition using the compound of the present invention as a latent additive had less outgassing, and the cured product was excellent in solvent resistance. [Industrial Applicability] According to the present invention, it is possible to provide a compound that is inert at normal temperature, activated by heating to a specific temperature, and exhibits a function as an antioxidant or an ultraviolet absorber with less outgassing And the photosensitive composition with high solvent resistance of hardened|cured material.

Figure 106110457-A0101-11-0002-2
Figure 106110457-A0101-11-0002-2

Claims (9)

一種感光性組合物，其含有具有下述通式(I)所表示之取代基之化合物(但二烯丙基醚雙酚A及二烯丙基醚雙酚S除外)，
Figure 106110457-A0305-02-0060-1
 (式中，R1及R2分別獨立地表示氫原子、鹵素原子、氰基、羥基、硝基、羧基、有具有取代基之情形之碳原子數1~40之烷基、有具有取代基之情形之碳原子數6~20之芳基、有具有取代基之情形之碳原子數7~20之芳基烷基、有具有取代基之情形之碳原子數2~20之含雜環之基或三烷基矽烷基，取代R1及R2所表示之碳原子數1~40之烷基、碳原子數6~20之芳基、碳原子數7~20之芳基烷基或碳原子數2~20之含雜環之基之取代基為乙烯性不飽和基、鹵素原子、醯基、醯氧基、取代胺基、磺醯胺基、磺醯基、羧基、氰基、磺基、羥基、硝基、巰基、醯亞胺基、胺甲醯基、磺醯胺基、膦酸基、磷酸基、羧基之鹽、磺基之鹽、膦酸基之鹽、或磷酸基之鹽，R1及R2所表示之烷基或芳基烷基中之亞甲基有被取代為於氧原子不相鄰之條件下將選自-O-、-S-、-CO-、-O-CO-、-CO-O-、-O-CO-O-、-S-CO-、-CO-S-、-S-CO-O-、-O-CO-S-、-CO-NH-、-NH-CO-、-NH-CO-O-、-NR'-、-S-S-或-SO2-中之基組合而成之基之情形，R'表示氫原子 或碳原子數1~8之烷基，j表示1~3之數，*意指於*部分與鄰接之基進行鍵結)。 A photosensitive composition containing a compound having a substituent represented by the following general formula (I) (except diallyl ether bisphenol A and diallyl ether bisphenol S),
Figure 106110457-A0305-02-0060-1
 (in the formula, R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms in the case of having a substituent, a group having a substituent In the case of an aryl group having 6 to 20 carbon atoms, in the case of having a substituent, an arylalkyl group having 7 to 20 carbon atoms, and in the case of having a substituent, a heterocyclic group containing 2 to 20 carbon atoms. Alkyl or trialkylsilyl group, substituted for the alkyl group with 1-40 carbon atoms, the aryl group with 6-20 carbon atoms, the arylalkyl group with 7-20 carbon atoms represented by R 1 and R 2 or the carbon atoms Substituents of heterocycle-containing groups having 2 to 20 atoms are ethylenically unsaturated groups, halogen atoms, acyl groups, acyloxy groups, substituted amino groups, sulfonamido groups, sulfonyl groups, carboxyl groups, cyano groups, sulfonic groups group, hydroxyl, nitro, mercapto, imino, carbamoyl, sulfonamido, phosphonic, phosphoric, carboxyl, sulfo, phosphonic, or phosphoric Salt, the methylene group in the alkyl or arylalkyl group represented by R 1 and R 2 has been substituted to be selected from -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO -NH-, -NH-CO-, -NH-CO-O-, -NR'-, -SS- or -SO 2 - in the case of a combination of groups, R' represents a hydrogen atom or a carbon atom An alkyl group of numbers 1 to 8, j represents a number of 1 to 3, and * means that the * part is bonded to an adjacent group). 如請求項1之感光性組合物，其中具有上述通式(I)所表示之取代基之化合物為下述通式(I-A)所表示之化合物，
Figure 106110457-A0305-02-0061-2
 (式中，n表示1~10之整數，X1表示n價鍵結基，R1、R2及j與上述通式(I)相同)。 The photosensitive composition according to claim 1, wherein the compound having the substituent represented by the above general formula (I) is a compound represented by the following general formula (IA),
Figure 106110457-A0305-02-0061-2
 (In the formula, n represents an integer of 1 to 10, X 1 represents an n-valent bonding group, and R 1 , R 2 and j are the same as the above-mentioned general formula (I).). 一種硬化物，其係如請求項1之感光性組合物之硬化物。 A hardened product, which is the hardened product of the photosensitive composition of claim 1. 一種顯示裝置，其至少一部分具備使用如請求項3之硬化物所形成之透明積層體或透明構造體。 A display device including at least a part of the transparent laminate or transparent structure formed using the cured product of claim 3. 一種著色感光性組合物，其係使如請求項1之感光性組合物中進而含有著色劑而成。 A colored photosensitive composition obtained by further containing a colorant in the photosensitive composition as claimed in claim 1. 一種硬化物，其係如請求項5之著色感光性組合物之硬化物。 A hardened product, which is the hardened product of the colored photosensitive composition of claim 5. 一種彩色濾光片，其係使用如請求項6之硬化物所形成。 A color filter formed using the hardened material as claimed in claim 6. 一種使如請求項1之感光性組合物或如請求項5之著色感光性組合物硬化之方法，其包括將如請求項1之感光性組合物或如請求項5之著色感光性組合物塗佈於支持基體上而形成塗膜之步驟、及對該塗膜曝光活性光而使其硬化之步驟。 A method of hardening the photosensitive composition as claimed in claim 1 or the colored photosensitive composition as claimed in claim 5, comprising applying the photosensitive composition as claimed in claim 1 or the colored photosensitive composition as claimed in claim 5 The step of forming a coating film by spreading on a support substrate, and the step of exposing the coating film to active light to harden it. 一種新穎化合物，其以下述結構(A)至(O)中之任一者表示，
Figure 106110457-A0305-02-0062-3
Figure 106110457-A0305-02-0063-4
 A novel compound represented by any one of the following structures (A) to (O),
Figure 106110457-A0305-02-0062-3
Figure 106110457-A0305-02-0063-4
TW106110457A 2016-03-31 2017-03-29 Photosensitive composition and novel compound TWI771294B (en)

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