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TWI798206B - Oxime ester compound and photopolymerization initiator containing the same - Google Patents

Oxime ester compound and photopolymerization initiator containing the same Download PDF

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TWI798206B
TWI798206B TW107108827A TW107108827A TWI798206B TW I798206 B TWI798206 B TW I798206B TW 107108827 A TW107108827 A TW 107108827A TW 107108827 A TW107108827 A TW 107108827A TW I798206 B TWI798206 B TW I798206B
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TW201838986A (en
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竹內良智
三原大樹
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日商艾迪科股份有限公司
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    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
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    • 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
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    • 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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    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

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Abstract

本發明係一種肟酯化合物，其以通式(Iα)或(Iβ)表示。

Figure 107108827-A0101-11-0001-1
(式中，R1 ～R6 及R101 ～R108 分別獨立地表示通式(II)所表示之基、氫原子、鹵素原子、硝基、氰基、羥基或羧基等，R1 ～R6 及R101 ～R108 中之任一者為通式(II)所表示之基，R7 ～R11 及R109 ～R113 分別獨立地表示通式(IIIα)或(IIIβ)所表示之基、氫原子、鹵素原子、硝基、氰基、羥基或羧基等，R7 ～R11 及R109 ～R113 中之至少一者為通式(IIIα)或(IIIβ)所表示之基，X1 及X101 表示不存在、直接鍵、-CO-、-O-或-S-(詳細情況參照說明書))。The present invention is an oxime ester compound represented by general formula (Iα) or (Iβ).
Figure 107108827-A0101-11-0001-1
(In the formula, R 1 to R 6 and R 101 to R 108 independently represent a group represented by the general formula (II), a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group or a carboxyl group, etc., and R 1 to R 6 and any one of R 101 to R 108 is a group represented by general formula (II), and R 7 to R 11 and R 109 to R 113 independently represent a group represented by general formula (IIIα) or (IIIβ). group, hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group or carboxyl group, etc., at least one of R 7 to R 11 and R 109 to R 113 is a group represented by general formula (IIIα) or (IIIβ), X1 and X101 represent absence, direct bond, -CO-, -O-, or -S- (for details, refer to the specification)).

Description

肟酯化合物及含有該化合物之光聚合起始劑Oxime ester compound and photopolymerization initiator containing the same

本發明係關於一種作為用於感光性組合物之光聚合起始劑有用之新穎之肟酯化合物、含有該化合物之光聚合起始劑、以及含有該光聚合起始劑及乙烯性不飽和化合物之感光性組合物。The present invention relates to a novel oxime ester compound useful as a photopolymerization initiator used in photosensitive compositions, a photopolymerization initiator containing the compound, and a photopolymerization initiator containing the photopolymerization initiator and an ethylenically unsaturated compound photosensitive composition.

感光性組合物由於係對乙烯性不飽和化合物加入光聚合起始劑而成者，且可藉由照射能量線(光)進行聚合硬化，故而被用於光硬化性油墨、感光性印刷版、各種光阻等。 作為上述用於感光性組合物之光聚合起始劑，於下述專利文獻1揭示有一種具有芳香族雜環之敏感性較高之肟酯光起始劑，於下述專利文獻2揭示有一種於365～405 nm中具有較大之吸收能之高感度之光聚合起始劑，於下述專利文獻3揭示有一種能夠達成高感度且高解像度之感光性組合物之光聚合起始劑。然而，於該等專利文獻所記載之肟酯化合物之感度並不一定能夠令人滿意，期待感度進一步提昇。 彩色濾光片等中所使用之含有著色劑之著色鹼性顯影性感光性樹脂組合物尤其要求為高感度，且需要將抗蝕劑中之光聚合起始劑設為高濃度。然而，高濃度之光聚合起始劑會引起如下情況：因顯影性之變差而引起殘渣之產生，或因昇華物而引起光罩或加熱爐之污染等。 又，於彩色濾光片等中使用之含有著色劑之著色鹼性顯影性感光性樹脂組合物中，亦要求使用之光聚合起始劑於可見光區域中具有較高之透過率。若可見光區域中之透過率較低，則產生亮度之降低等問題。 進而，光聚合起始劑由於於用於各種用途時係溶解於有機溶劑中而使用，故而亦要求於有機溶劑中之溶解性較高。 先前技術文獻 專利文獻 專利文獻1：美國專利申請公開第2006/241259號說明書 專利文獻2：日本專利特開2014-009325號公報 專利文獻3：日本專利特開2014-159390號公報The photosensitive composition is made by adding a photopolymerization initiator to an ethylenically unsaturated compound, and can be polymerized and hardened by irradiating energy rays (light), so it is used for photocurable inks, photosensitive printing plates, Various photoresists, etc. As the above-mentioned photopolymerization initiator used in the photosensitive composition, the following patent document 1 discloses a highly sensitive oxime ester photoinitiator having an aromatic heterocycle, and the following patent document 2 discloses A high-sensitivity photopolymerization initiator having a large absorption energy at 365-405 nm, a photopolymerization initiator capable of achieving a high-sensitivity and high-resolution photosensitive composition is disclosed in the following patent document 3 . However, the sensitivity of the oxime ester compounds described in these patent documents is not necessarily satisfactory, and the sensitivity is expected to be further improved. In particular, the colored alkali-developable photosensitive resin composition containing a colorant used in color filters and the like is required to have high sensitivity, and it is necessary to have a high concentration of the photopolymerization initiator in the resist. However, a high concentration of the photopolymerization initiator will cause the following situations: the generation of residue due to the deterioration of the developability, or the pollution of the photomask or the heating furnace due to the sublimation. Moreover, in the colored alkali-developable photosensitive resin composition containing the coloring agent used for a color filter etc., the photopolymerization initiator used is also required to have a high transmittance in the visible light region. If the transmittance in the visible light region is low, there will be problems such as a decrease in luminance. Furthermore, since a photoinitiator is used by being dissolved in an organic solvent when it uses for various uses, high solubility in an organic solvent is also required. Prior Art Documents Patent Documents Patent Document 1: Specification of US Patent Application Publication No. 2006/241259 Patent Document 2: Japanese Patent Laid-Open No. 2014-009325 Patent Document 3: Japanese Patent Laid-Open No. 2014-159390

欲解決之問題點在於：到目前為止尚無具有能夠令人滿意之感度、於有機溶劑中之溶解性較高、且可見光區域之透過率較高之光聚合起始劑。 因此，本發明之目的在於提供一種新穎之化合物、及使用該化合物之光聚合起始劑、以及感光性組合物，該化合物為高效率地吸收365 nm等之近紫外線光並進行活化之高感度之化合物，於有機溶劑中之溶解性較高，進而可見光區域之透過率亦較高，作為光聚合起始劑有用。 本發明藉由提供下述[1]～[11]而達成上述目的。 [1]一種肟酯化合物，其以下述通式(Iα)或(Iβ)表示。 [化1]

Figure 02_image007
(式中，R1 、R2 、R3 、R4 、R5 及R6 分別獨立地表示下述通式(II)所表示之基、氫原子、鹵素原子、硝基、氰基、羥基、羧基、R21 、OR21 、SR21 、NR22 R23 、COR21 、SOR21 、SO2 R21 或CONR22 R23 ； R1 、R2 、R3 、R4 、R5 及R6 中之至少一者為下述通式(II)所表示之基； R7 、R8 、R9 、R10 及R11 分別獨立地表示下述通式(IIIα)所表示之基、下述通式(IIIβ)所表示之基、氫原子、鹵素原子、硝基、氰基、羥基、羧基、R21 、OR21 、SR21 、NR22 R23 、COR21 、SOR21 、SO2 R21 或CONR22 R23 ； R7 、R8 、R9 、R10 及R11 中之至少一者為下述通式(IIIα)所表示之基或下述通式(IIIβ)所表示之基； R21 、R22 及R23 分別獨立地表示碳原子數1～20之烴基或碳原子數2～20之含雜環之基； R21 、R22 及R23 所表示之基中之氫原子有時被取代為鹵素原子、硝基、氰基、羥基、胺基、羧基、甲基丙烯醯基、丙烯醯基、環氧基、乙烯基、乙烯醚基、巰基、異氰酸基或含雜環之基，碳原子數2～20之烴基或碳原子數2～20之含雜環之基中之亞甲基有時被取代為-O-、-CO-、-COO-、-OCO-、-NR24 -、-NR24 CO-、-S-、-CS-、-SO2 -、-SCO-、-COS-、-OCS-或CSO-，R24 表示氫原子或碳原子數1～20之烴基； X1 表示不存在、直接鍵、-CO-、-O-或-S-； R1 與R2 、R2 與R3 、R3 與R4 、R5 與R6 、R6 與R7 、R7 與R8 、R8 與R9 、R9 與R10 、R10 與R11 、及R11 與R1 有時進行鍵結而形成環)。 [化2]
Figure 02_image009
(式中，R31 及R32 分別獨立地表示氫原子、鹵素原子、硝基、氰基、碳原子數1～20之烴基或碳原子數2～20之含雜環之基； R31 及R32 所表示之碳原子數1～20之烴基或碳原子數2～20之含雜環之基之氫原子有時被取代為鹵素原子、硝基、氰基、羥基、胺基、羧基、甲基丙烯醯基、丙烯醯基、環氧基、乙烯基、乙烯醚基、巰基、異氰酸基或含雜環之基，R31 及R32 所表示之碳原子數2～20之烴基或碳原子數2～20之含雜環之基中之亞甲基有時被取代為-O-、-CO-、-COO-、-OCO-、-NR33 -、-NR33 CO-、-S-、-CS-、-SO2 -、-SCO-、-COS-、-OCS-或CSO-，R33 表示氫原子或碳原子數1～20之烴基； n表示0或1，*表示鍵結鍵)。 [化3]
Figure 02_image011
(式中，R41 、R42 、R43 、R44 、R45 、R46 、R47 、R48 、R49 及R50 分別獨立地表示氫原子、鹵素原子、硝基、氰基、羥基、羧基、R51 、OR51 、SR51 、NR52 R53 、COR51 、SOR51 、SO2 R51 或CONR52 R53 ； R51 、R52 及R53 分別獨立地表示碳原子數1～20之烴基或碳原子數2～20之含雜環之基； R51 、R52 及R53 所表示之基中之氫原子有時被取代為鹵素原子、硝基、氰基、羥基、胺基、羧基、甲基丙烯醯基、丙烯醯基、環氧基、乙烯基、乙烯醚基、巰基、異氰酸基或含雜環之基，碳原子數2～20之烴基或碳原子數2～20之含雜環之基中之亞甲基有時被取代為-O-、-CO-、-COO-、-OCO-、-NR54 -、-NR54 CO-、-S-、-CS-、-SO2 -、-SCO-、-COS-、-OCS-或CSO-； X2 及X3 表示-O-、-S-或-NR54 -； R54 表示氫原子或碳原子數1～20之烴基； *表示鍵結鍵)。 [化3A]
Figure 02_image013
(式中，R101 、R102 、R103 、R104 、R105 、R106 、R107 及R108 分別獨立地表示上述通式(II)所表示之基、氫原子、鹵素原子、硝基、氰基、羥基、羧基、R121 、OR121 、SR121 、NR122 R123 、COR121 、SOR121 、SO2 R121 或CONR122 R123 ； R101 、R102 、R103 、R104 、R105 、R106 、R107 及R108 中之至少一者為上述通式(II)所表示之基； R109 、R110 、R111 、R112 及R113 分別獨立地表示上述通式(IIIα)所表示之基、上述通式(IIIβ)所表示之基、氫原子、鹵素原子、硝基、氰基、羥基、羧基、R121 、OR121 、SR121 、NR122 R123 、COR121 、SOR121 、SO2 R121 或CONR122 R123 ； R109 、R110 、R111 、R112 及R113 中之至少一者為下述通式(IIIα)所表示之基或下述通式(IIIβ)所表示之基； R121 、R122 及R123 分別獨立地表示碳原子數1～20之烴基或碳原子數2～20之含雜環之基； R121 、R122 及R123 所表示之基中之氫原子有時被取代為鹵素原子、硝基、氰基、羥基、胺基、羧基、甲基丙烯醯基、丙烯醯基、環氧基、乙烯基、乙烯醚基、巰基、異氰酸基或含雜環之基，碳原子數2～20之烴基或碳原子數2～20之含雜環之基中之亞甲基有時被取代為-O-、-CO-、-COO-、-OCO-、-NR124 -、-NR124 CO-、-S-、-CS-、-SO2 -、-SCO-、-COS-、-OCS-或CSO-； R124 表示氫原子或碳原子數1～20之烴基； X101 表示不存在、直接鍵、-CO-、-O-或-S-； R101 與R102 、R102 與R103 、R103 與R104 、R105 與R106 、R106 與R107 、R107 與R108 、R108 與R109 、R109 與R110 、R110 與R111 、R111 與R112 、R112 與R113 及R113 與R101 有時進行鍵結而形成環)。 [2]如[1]所記載之肟酯化合物，其中通式(Iα)中之R3 及R5 之中至少一者為通式(II)所表示之基。 [3]如[1]所記載之肟酯化合物，其中通式(Iβ)中之R103 及R106 之中至少一者為通式(II)所表示之基。 [4]如[1]或[2]所記載之肟酯化合物，其中通式(Iα)中之X1 不存在且R5 與R6 鍵結而形成苯環。 [5]一種光聚合起始劑，其含有如[1]～[4]中任一項所記載之肟酯化合物。 [6]一種感光性組合物，其含有如[5]所記載之光聚合起始劑(A)及乙烯性不飽和化合物(B)。 [7]如[6]所記載之感光性組合物，其進而含有著色劑(C)。 [8]一種鹼性顯影性感光性樹脂組合物，其係使如[6]或[7]所記載之感光性組合物含有鹼性顯影性化合物(D)而成。 [9]一種硬化物，其係如[6]或[7]所記載之感光性組合物或如[8]所記載之鹼性顯影性感光性樹脂組合物之硬化物。 [10]一種顯示器顯示裝置，其含有如[9]所記載之硬化物。 [11]一種硬化物之製造方法，其具有如下步驟：使用如[6]或[7]記載之感光性組合物或如[8]記載之鹼性顯影性感光性樹脂組合物，使該組合物硬化。The problem to be solved is: so far there is no photopolymerization initiator with satisfactory sensitivity, high solubility in organic solvents, and high transmittance in the visible light region. Therefore, the object of the present invention is to provide a novel compound, a photopolymerization initiator using the compound, and a photosensitive composition. The compound has high solubility in organic solvents and high transmittance in the visible light region, and is useful as a photopolymerization initiator. The present invention achieves the above object by providing the following [1] to [11]. [1] An oxime ester compound represented by the following general formula (Iα) or (Iβ). [chemical 1]
Figure 02_image007
(In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently represent a group represented by the following general formula (II), a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group , carboxyl, R 21 , OR 21 , SR 21 , NR 22 R 23 , COR 21 , SOR 21 , SO 2 R 21 or CONR 22 R 23 ; R 1 , R 2 , R 3 , R 4 , R 5 and R 6 At least one of them is a group represented by the following general formula (II); R 7 , R 8 , R 9 , R 10 and R 11 each independently represent a group represented by the following general formula (IIIα), the following Group represented by general formula (IIIβ), hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, R 21 , OR 21 , SR 21 , NR 22 R 23 , COR 21 , SOR 21 , SO 2 R 21 or CONR 22 R 23 ; at least one of R 7 , R 8 , R 9 , R 10 and R 11 is a group represented by the following general formula (IIIα) or a group represented by the following general formula (IIIβ); R 21 , R 22 and R 23 independently represent a hydrocarbon group with 1 to 20 carbon atoms or a heterocyclic group with 2 to 20 carbon atoms; hydrogen atoms in the groups represented by R 21 , R 22 and R 23 Sometimes substituted by halogen atom, nitro group, cyano group, hydroxyl group, amine group, carboxyl group, methacryl group, acryl group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group or containing As a heterocyclic group, a hydrocarbon group with 2 to 20 carbon atoms or a heterocyclic group with 2 to 20 carbon atoms, the methylene group is sometimes substituted with -O-, -CO-, -COO-, -OCO -, -NR 24 -, -NR 24 CO-, -S-, -CS-, -SO 2 -, -SCO-, -COS-, -OCS- or CSO-, R 24 represents the number of hydrogen atoms or carbon atoms 1 to 20 hydrocarbon groups; X 1 represents absence, direct bond, -CO-, -O- or -S-; R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , R 9 and R 10 , R 10 and R 11 , and R 11 and R 1 may bond to form a ring). [Chem 2]
Figure 02_image009
(wherein, R 31 and R 32 independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group with 1 to 20 carbon atoms or a heterocyclic group with 2 to 20 carbon atoms; R 31 and The hydrogen atom of the hydrocarbon group with 1 to 20 carbon atoms or the heterocyclic group with 2 to 20 carbon atoms represented by R32 is sometimes substituted by a halogen atom, nitro, cyano, hydroxyl, amino, carboxyl, Methacryl group, acryl group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group or a group containing a heterocycle, a hydrocarbon group with 2 to 20 carbon atoms represented by R31 and R32 Or the methylene group in the heterocyclic ring-containing group with 2 to 20 carbon atoms may be substituted with -O-, -CO-, -COO-, -OCO-, -NR 33 -, -NR 33 CO-, -S-, -CS-, -SO 2 -, -SCO-, -COS-, -OCS- or CSO-, R 33 represents a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms; n represents 0 or 1, * represents a bonded key). [Chem 3]
Figure 02_image011
(wherein, R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 and R 50 independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group , carboxyl, R 51 , OR 51 , SR 51 , NR 52 R 53 , COR 51 , SOR 51 , SO 2 R 51 or CONR 52 R 53 ; R 51 , R 52 and R 53 independently represent carbon atoms of 1 to A hydrocarbon group with 20 carbon atoms or a heterocyclic group with 2 to 20 carbon atoms; the hydrogen atoms in the groups represented by R 51 , R 52 and R 53 are sometimes substituted by halogen atoms, nitro groups, cyano groups, hydroxyl groups, and amines group, carboxyl group, methacryl group, acryl group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group or a group containing a heterocyclic ring, a hydrocarbon group with 2 to 20 carbon atoms or a carbon number The methylene group in the heterocycle-containing group of 2 to 20 is sometimes substituted by -O-, -CO-, -COO-, -OCO-, -NR 54 -, -NR 54 CO-, -S-, -CS-, -SO 2 -, -SCO-, -COS-, -OCS- or CSO-; X 2 and X 3 represent -O-, -S- or -NR 54 -; R 54 represents a hydrogen atom or carbon A hydrocarbon group with 1 to 20 atoms; * indicates a bonding bond). [Chem3A]
Figure 02_image013
(wherein, R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 and R 108 independently represent the group represented by the above general formula (II), hydrogen atom, halogen atom, nitro group , cyano, hydroxyl, carboxyl, R 121 , OR 121 , SR 121 , NR 122 R 123 , COR 121 , SOR 121 , SO 2 R 121 or CONR 122 R 123 ; R 101 , R 102 , R 103 , R 104 , At least one of R 105 , R 106 , R 107 and R 108 is a group represented by the above general formula (II); R 109 , R 110 , R 111 , R 112 and R 113 independently represent the above general formula ( A group represented by IIIα), a group represented by the above general formula (IIIβ), a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, R 121 , OR 121 , SR 121 , NR 122 R 123 , COR 121 , SOR 121 , SO 2 R 121 or CONR 122 R 123 ; at least one of R 109 , R 110 , R 111 , R 112 and R 113 is the group represented by the following general formula (IIIα) or the following general formula The group represented by (IIIβ); R 121 , R 122 and R 123 independently represent a hydrocarbon group with 1 to 20 carbon atoms or a heterocyclic group with 2 to 20 carbon atoms; R 121 , R 122 and R 123 The hydrogen atom in the group represented is sometimes replaced by a halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, methacryl group, acryl group, epoxy group, vinyl group, vinyl ether group, Mercapto, isocyanate or heterocyclic group, the methylene group in the hydrocarbon group with 2 to 20 carbon atoms or the heterocyclic group with 2 to 20 carbon atoms is sometimes substituted with -O-, -CO -, -COO-, -OCO-, -NR 124 -, -NR 124 CO-, -S-, -CS-, -SO 2 -, -SCO-, -COS-, -OCS- or CSO-; R 124 represents a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms; X 101 represents absence, direct bond, -CO-, -O- or -S-; R 101 and R 102 , R 102 and R 103 , R 103 and R 104 , R 105 and R 106 , R 106 and R 107 , R 107 and R 108 , R 108 and R 109 , R 109 and R 110 , R 110 and R 111 , R 111 and R 112 , R 112 and R 113 And R 113 and R 101 are sometimes bonded to form a ring). [2] The oxime ester compound as described in [1], wherein at least one of R 3 and R 5 in the general formula (Iα) is a group represented by the general formula (II). [3] The oxime ester compound as described in [1], wherein at least one of R 103 and R 106 in the general formula (Iβ) is a group represented by the general formula (II). [4] The oxime ester compound as described in [1] or [2], wherein X 1 in the general formula (Iα) does not exist and R 5 and R 6 are bonded to form a benzene ring. [5] A photopolymerization initiator containing the oxime ester compound according to any one of [1] to [4]. [6] A photosensitive composition containing the photopolymerization initiator (A) and the ethylenically unsaturated compound (B) as described in [5]. [7] The photosensitive composition as described in [6] which further contains a coloring agent (C). [8] An alkali-developable photosensitive resin composition comprising an alkali-developable compound (D) contained in the photosensitive composition as described in [6] or [7]. [9] A cured product of the photosensitive composition as described in [6] or [7] or the cured product of the alkali-developable photosensitive resin composition as described in [8]. [10] A display device comprising the cured product described in [9]. [11] A method for producing a cured product, comprising the steps of: using the photosensitive composition described in [6] or [7] or the alkali-developable photosensitive resin composition described in [8], making the composition material hardening.

以下，針對含有本發明之肟酯化合物及該化合物之本發明之光聚合起始劑，基於較佳之實施形態詳細地進行說明。 本發明之肟酯化合物係上述通式(Iα)或(Iβ)所表示之新穎之化合物。該肟酯化合物存在由肟之雙鍵而產生之幾何異構物，但本發明並不對該等加以區別。 即，於本說明書中，上述通式(Iα)或(Iβ)所表示之化合物及其例示化合物表示該等幾何異構物之1種或2種以上之混合物，並不限定於示出結構之特定之異構物。 上述通式(Iα)中之R21 ～R24 、及上述通式(Iβ)中之R121 ～R124 所表示之碳原子數1～20之烴基並無特別限定，較佳為表示碳原子數1～20之烷基、碳原子數2～20之烯基、碳原子數3～20之環烷基、碳原子數4～20之環烷基烷基、碳原子數6～20之芳基及碳原子數7～20之芳烷基等。 作為上述碳原子數1～20之烷基，例如可列舉：甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、異戊基、第三戊基、己基、庚基、辛基、異辛基、2-乙基己基、第三辛基、壬基、異壬基、癸基、異癸基、十一烷基、十二烷基、十四烷基、十六烷基、十八烷基及二十烷基等。 作為碳原子數2～20之烯基，例如可列舉：乙烯基、伸乙基、2-丙烯基、3-丁烯基、2-丁烯基、4-戊烯基、3-戊烯基、2-己烯基、3-己烯基、5-己烯基、2-庚烯基、3-庚烯基、4-庚烯基、3-辛烯基、3-壬烯基、4-癸烯基、3-十一碳烯基、4-十二碳烯基及4,8,12-十四碳三烯-1-基烯丙基等。 上述所謂碳原子數3～20之環烷基，意指具有3～20個碳原子之飽和單環式或飽和多環式烷基。例如可列舉：環丙基、環丁基、環戊基、環己基、環庚基、環辛基、環壬基、環癸基、金剛烷基、十氫萘基、八氫并環戊二烯及雙環[1.1.1]戊基等。 上述所謂碳原子數4～20之環烷基烷基，意指烷基之氫原子經環烷基取代之具有4～20個碳原子之基。例如可列舉：環丙基甲基、2-環丁基乙基、3-環戊基丙基、4-環己基丁基、環庚基甲基、環辛基甲基、2-環壬基乙基、2-環癸基乙基、3-3-金剛烷基丙基及十氫萘基丙基等。 作為上述碳原子數6～20之芳基，例如可列舉：苯基、甲苯基、二甲苯基、乙基苯基、萘基、蒽基、菲基、經1個以上上述烷基取代之苯基、聯苯基、萘基、蒽基等。 上述所謂碳原子數7～20之芳烷基，意指烷基之氫原子經芳基取代之具有7～20之碳原子之基。例如可列舉：苄基、α-甲基苄基、α,α-二甲基苄基、苯基乙基及萘基丙基等。 上述碳原子數1～20之烴基之中，就作為光聚合起始劑而言感度較佳之方面而言，尤佳為碳原子數1～12之烷基、碳原子數2～10之烯基、碳原子數3～10之環烷基、碳原子數4～15之環烷基烷基、碳原子數6～15之芳基及碳原子數7～15之芳烷基。 作為上述通式(Iα)中之R21 ～R23 、及上述通式(Iβ)中之R121 ～R123 所表示之碳原子數2～20之含雜環之基，例如可列舉：吡咯基、吡啶基、吡啶基乙基、嘧啶基、嗒𠯤基、哌𠯤基、哌啶基、吡喃基、吡喃基乙基、吡唑基、三𠯤基、三𠯤基甲基、吡咯啶基、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(benzofuranyl)、噻吩基(thienyl)、噻吩基(thiophenyl)、苯并噻吩基(benzothiophenyl)、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、𠮻咯啶基、嗎啉基、硫代嗎啉基、2-吡咯啶酮-1-基、2-哌啶酮-1-基、2,4-二氧基咪唑啶-3-基及2,4-二氧基㗁唑啶-3-基等。 上述碳原子數2～20之含雜環之基之中，尤佳為碳原子數2～10之含雜環之基，其原因在於製成光聚合起始劑感度較佳。 上述通式(Iα)中之R21 ～R23 所表示之基中之亞甲基有時被取代為-O-、-CO-、-COO-、-OCO-、-NR24 -、-NR24 CO-、-S-、-CS-、-SO2 -、-SCO-、-COS-、-OCS-或CSO-，又，上述通式(Iβ)中之R121 ～R123 所表示之基中之亞甲基有時被取代為-O-、-CO-、-COO-、-OCO-、-NR124 -、-NR124 CO-、-S-、-CS-、-SO2 -、-SCO-、-COS-、-OCS-或CSO-，該等取代係利用1種或2種以上之基進行者，於可連續地取代之基之情形時，有時於氧原子不相鄰之條件下被2個以上之基連續地取代。 作為R1 與R2 、R2 與R3 、R3 與R4 、R5 與R6 、R6 與R7 、R7 與R8 、R8 與R9 、R9 與R10 、R10 與R11 、R11 與R1 、R101 與R102 、R102 與R103 、R103 與R104 、R105 與R106 、R106 與R107 、R107 與R108 、R108 與R109 、R109 與R110 、R110 與R111 、R111 與R112 、R112 與R113 及R113 與R101 鍵結所形成之環，例如可列舉：環戊烷、環己烷、環戊烯、苯、吡咯啶、吡咯、哌𠯤、嗎啉、硫代嗎啉、四氫吡啶、內酯環及內醯胺環等5～7員環以及萘及蒽等縮合環等。 作為上述通式(II)中之R31 ～R33 所表示之碳原子數1～20之烴基，可列舉與上述通式(Iα)中之R21 ～R24 或上述通式(Iβ)中之R121 ～R124 所表示之碳原子數1～20之烴基相同者。 作為上述通式(II)中之R31 及R32 所表示之碳原子數2～20之含雜環之基，可列舉與上述通式(Iα)中之R21 ～R23 及上述通式(Iβ)中之R121 ～R123 所表示之碳原子數2～20之含雜環之基相同者。 上述通式(II)中之R31 及R32 所表示之基中之亞甲基有時被取代為-O-、-CO-、-COO-、-OCO-、-NR33 -、-NR33 CO-、-S-、-CS-、-SO2 -、-SCO-、-COS-、-OCS-或CSO-，該取代係利用1種或2種以上基進行者，於可連續地取代之基之情形時，有時於氧原子不相鄰之條件下被2個以上之基連續地取代。 作為上述通式(IIIα)及(IIIβ)中之R51 ～R54 所表示之碳原子數1～20之烴基，可列舉與上述通式(Iα)中之R21 ～R24 及上述通式(Iβ)中之R121 ～R124 所表示之碳原子數1～20之烴基相同者。 作為上述通式(IIIα)及(IIIβ)中之R51 ～R53 所表示之碳原子數2～20之含雜環之基，可列舉與上述通式(Iα)中之R21 ～R23 及上述通式(Iβ)中之R121 ～R123 所表示之碳原子數2～20之含雜環之基相同者。 作為上述通式(Iα)、(Iβ)、(II)、(IIIα)及(IIIβ)中之鹵素原子，可列舉：氟、氯、溴、碘。 本發明之肟酯化合物中，通式(Iα)中之R3 及R5 之至少一者為通式(II)所表示之基之肟酯化合物就合成時產率良好且亦容易進行精製之方面而言較佳。 又，本發明之肟酯化合物之中，通式(Iβ)中之R103 及R106 之至少一者為通式(II)所表示之基之肟酯化合物就合成時產率良好且亦容易進行精製之方面而言較佳。就相同之觀點而言，亦較佳為通式(Iβ)中之R103 及R106 之兩者為通式(II)所表示之基的肟酯化合物。 於上述通式(Iα)及(Iβ)中，於R1 及R101 為除通式(II)所表示之基以外之基或原子之情形時，R1 及R101 為氫原子或氰基、尤其是氫原子者由於容易合成故而較佳。關於R2 ～R5 及R102 ～R107 各者，亦與R1 相同。即，於R2 ～R5 及R102 ～R106 為除通式(II)所表示之基以外之基或原子之情形時，若R2 ～R5 及R102 ～R106 為氫原子或氰基、尤其是氫原子，則容易合成，故而較佳。 又，於上述通式(Iα)及(Iβ)中，於R6 及R108 為除通式(II)所表示之基以外之基或原子之情形時，R6 及R108 為氫原子者由於容易合成故而較佳。 本發明之肟酯化合物之中，通式(Iα)中之X1 不存在且R5 與R6 鍵結而形成苯環之肟酯化合物就可高效率地吸收近紫外線光(尤其是365 nm)之方面而言較佳。 再者，於本說明書中，所謂「X1 不存在」，意指於通式(Iα)中不存在-X1 -所表示之鍵且未形成包含N原子及X1 之縮合環骨架之狀態。例如，上述「X1 不存在且R5 與R6 鍵結而形成苯環之肟酯化合物」為具有三苯胺骨架而並非包含N原子及X1 之縮合環骨架之化合物，作為該化合物之具體例，可列舉下述之化合物No.153～170。 又，通式(Iβ)中之所謂「X101 不存在」，意指不存在-X101 -所表示之鍵且未形成有包含N原子及X101 之縮合環骨架之狀態。 於上述通式(II)中，較佳為R31 為碳原子數1～12之烷基，其原因在於：於有機溶劑中之溶解性較高。又，由於反應性變高，因此於上述通式(II)中，較佳為R32 為甲基及乙基等碳原子數1～4之烷基或苯基，更佳為碳原子數1～4之烷基，尤佳為甲基。 於上述通式(Iα)所表示之本發明之肟酯化合物中，較佳為R9 為上述通式(IIIα)所表示之基。又，於上述通式(Iα)所表示之本發明之肟酯化合物中，較佳為R9 為上述通式(IIIβ)所表示之基。 於上述通式(Iβ)所表示之本發明之肟酯化合物中，較佳為R111 為上述通式(IIIα)所表示之基。又，於上述通式(Iβ)所表示之本發明之肟酯化合物中，較佳為R111 為上述通式(IIIβ)所表示之基。 上述通式(IIIα)所表示之基中之X2 較佳為氧原子或硫原子，尤佳為氧原子。其原因在於：肟酯化合物成為高效率地吸收長波長之近紫外線光者，作為光聚合起始劑成為高感度。上述通式(IIIα)所表示之基中之R41 ～R45 較佳為氫原子。 上述通式(IIIβ)所表示之基中之X3 較佳為氧原子或硫原子。其原因在於：肟酯化合物成為高效率地吸收長波長之近紫外線光者，作為光聚合起始劑成為高感度。上述通式(IIIβ)所表示之基中之R46 ～R50 較佳為氫原子。 於上述通式(Iα)所表示之本發明之肟酯化合物中，較佳為X1 不存在。 於上述通式(Iβ)所表示之本發明之肟酯化合物中，較佳為X101 不存在，亦較佳為X101 為硫。 作為上述通式(Iα)或(Iβ)所表示之本發明之肟酯化合物之較佳之具體例，可列舉以下化合物No.1～No.194。但是，本發明絲毫不受以下化合物所限制。 [化4]

Figure 02_image015
Figure 02_image017
[化5]
Figure 02_image019
[化6]
Figure 02_image021
[化7]
Figure 02_image023
[化8]
Figure 02_image025
[化9]
Figure 02_image027
[化10]
Figure 02_image029
[化11]
Figure 02_image031
[化12]
Figure 02_image033
[化13]
Figure 02_image035
[化14]
Figure 02_image037
[化15]
Figure 02_image039
[化16]
Figure 02_image041
[化17]
Figure 02_image043
[化18]
Figure 02_image045
[化19]
Figure 02_image047
[化20]
Figure 02_image049
[化21]
Figure 02_image051
[化22]
Figure 02_image053
[化23]
Figure 02_image055
[化24]
Figure 02_image057
[化25]
Figure 02_image059
[化25A]
Figure 02_image061
上述通式(Iα)或(Iβ)所表示之本發明之肟酯化合物並無特別限定，例如可利用下述所示之方法進行合成。 首先，獲得本發明之肟酯化合物之中間物即N-芳基化合物。該N-芳基化合物之合成法之一例如下。 即，藉由使用碳酸鉀使公知且正市售之醛化合物與公知且正市售之氟化苯化合物進行反應而獲得鹵化芳基化合物，並藉由使鹵化芳基化合物與公知且正市售之含N雜環化合物進行反應而獲得N-芳基化合物。 [化26]
Figure 02_image063
繼而，於通式(II)中之n為0之情形時，可使用上述N-芳基化合物，並根據下述反應式藉由以下方法而製造本發明之肟化合物。 即，藉由使上述N-芳基化合物與醯氯進行反應而獲得酮化合物1，並藉由使酮化合物1與鹽酸羥胺進行反應而獲得肟化合物1。繼而，藉由使酸酐或醯氯與肟化合物1進行反應而獲得上述通式(Iα)或(Iβ)所表示之本發明之肟酯化合物1。 再者，肟化合物1及肟酯化合物1亦可利用日本專利第4223071號公報記載之方法而製造。 [化27]
Figure 02_image065
又，於通式(II)中之n為1之情形時，可使用上述N-芳基化合物，並根據下述反應式藉由以下方法而製造本發明之肟化合物。 即，藉由使上述N-芳基化合物與醯氯進行反應而獲得酮化合物2，並藉由使亞硝酸異丁酯與酮化合物2進行反應而獲得肟化合物2。繼而，藉由使酸酐或醯氯與肟化合物2進行反應，而獲得上述通式(Iα)或(Iβ)所表示之本發明之肟酯化合物2。 [化28]
Figure 02_image067
再者，於該等反應式中，預先使醯氯與上述含N雜環化合物進行反應而製作含N雜環化合物之酮體，使該酮體代替上述含N雜環化合物與上述鹵化芳基化合物進行反應，藉此亦可獲得酮化合物1或2。 以上所說明之本發明之新穎之肟酯化合物作為自由基聚合起始劑、尤其是光聚合起始劑或熱聚合起始劑有用。又，本發明之新穎之肟酯化合物亦可較佳地用作增感劑。 本發明之光聚合起始劑係含有至少1種本發明之肟酯化合物者，可進而含有其他光聚合起始劑。光聚合起始劑中之本發明之肟酯化合物之含量較佳為30～100質量%，更佳為50～100質量%。 本發明之光聚合起始劑係作為乙烯性不飽和化合物之光聚合起始劑有用者。 作為可併用之其他光聚合起始劑，可使用先前既知之化合物，例如可列舉：二苯甲酮、苯基聯苯基甲酮、1-羥基-1-苯甲醯基環己烷、安息香、苯偶醯二甲基縮酮、1-苄基-1-二甲胺基-1-(4'-嗎啉基苯甲醯基)丙烷、2-嗎啉基-2-(4'-甲基巰基)苯甲醯基丙烷、9-氧硫
Figure 107108827-A0304-12-0019-1
Figure 107108827-A0304-xxxx-3
、1-氯-4-丙氧基9-氧硫
Figure 107108827-A0304-12-0019-1
Figure 107108827-A0304-xxxx-3
、異丙基9-氧硫
Figure 107108827-A0304-12-0019-1
Figure 107108827-A0304-xxxx-3
、二乙基9-氧硫
Figure 107108827-A0304-12-0019-1
Figure 107108827-A0304-xxxx-3
、乙基蒽醌、4-苯甲醯基-4'-甲基二苯基硫醚、安息香丁醚、2-羥基-2-苯甲醯基丙烷、2-羥基-2-(4'-異丙基)苯甲醯基丙烷、4-丁基苯甲醯基三氯甲烷、4-苯氧基苯甲醯基二氯甲烷、苯甲醯基甲酸甲酯、1,7-雙(9'-吖啶基)庚烷、9-正丁基-3,6-雙(2'-嗎啉基異丁醯基)咔唑、2-甲基-4,6-雙(三氯甲基)-均三𠯤、2-苯基-4,6-雙(三氯甲基)-均三𠯤、2-萘基-4,6-雙(三氯甲基)-均三𠯤、2,2-雙(2-氯苯基)-4,5,4',5'-四苯基-1-2'-聯咪唑、4,4-偶氮雙異丁腈、三苯基膦、樟腦醌、N-1414、N-1717、N-1919、NCI-831、NCI-930(ADEKA公司製造)、IRGACURE369、IRGACURE907、IRGACURE OXE 01、IRGACURE OXE 02(BASF公司製造)、過氧化苯甲醯基、下述通式(IV)所表示之化合物等。再者，該等光聚合起始劑可使用1種或將2種以上組合使用。 [化29]
Figure 02_image069
(式中，R61 及R62 分別獨立地表示氰基、碳原子數1～20之烷基、碳原子數6～30之芳基、碳原子數7～30之芳烷基或碳原子數2～20之雜環基； R63 及R64 分別獨立地表示鹵素原子、硝基、氰基、羥基、羧基、R65 、OR66 、SR67 、NR68 R69 、COR70 、SOR71 、SO2 R72 或CONR73 R74 ； R63 及R64 有時相互鍵結而形成環； R63 及R64 於分別存在複數個之情形時，有時相同亦有時不同； R65 、R66 、R67 、R68 、R69 、R70 、R71 、R72 、R73 及R74 分別獨立地表示碳原子數1～20之烷基、碳原子數6～30之芳基、碳原子數7～30之芳烷基或碳原子數2～20之雜環基； X4 表示直接鍵或CO； X5 表示氧原子、硫原子、硒原子、CR75 R76 、CO、或PR77 ； R75 、R76 及R77 分別獨立地表示碳原子數1～20之烷基、碳原子數6～30之芳基或碳原子數7～30之芳烷基； 該烷基或芳烷基中之氫原子有時被取代為鹵素原子、硝基、氰基、羥基、羧基或雜環基； 該烷基或芳烷基中之亞甲基有時被取代為-O-； a表示0～4之整數； b表示0～5之整數)。 繼而，針對本發明之感光性組合物進行說明。 本發明之感光性組合物係含有本發明之光聚合起始劑(A)及乙烯性不飽和化合物(B)且組合含有著色劑(C)、鹼性顯影性化合物(D)、溶劑、或後述任意之添加物作為任意成分者。 於本發明之感光性組合物中，光聚合起始劑(A)之含量並無特別限定，相對於乙烯性不飽和化合物(B)100質量份，較佳為1～70質量份，更佳為1～50質量份，最佳為5～30質量份。 上述乙烯性不飽和化合物(B)只要具有乙烯性之不飽和鍵，則並無特別限定，可使用先前用於感光性組合物者。例如可列舉：乙烯、丙烯、丁烯、異丁烯、氯乙烯、偏二氯乙烯、偏二氟乙烯、四氟乙烯等不飽和脂肪族烴；(甲基)丙烯酸、α-氯丙烯酸、伊康酸、順丁烯二酸、檸康酸、反丁烯二酸、雙環庚烯二甲酸、丁烯酸、異丁烯酸、乙烯乙酸、烯丙基乙酸、桂皮酸、山梨酸、中康酸、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)丙烯酸酯等兩末端具有羧基及羥基之聚合物之單(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個羧基及2個以上(甲基)丙烯醯基之多官能(甲基)丙烯酸酯等不飽和多元酸；(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)丙烯酸二甲胺基甲酯、(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸胺基丙酯、(甲基)丙烯酸二甲胺基丙酯、(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)丙烯酸乙酯己酯、(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、二新戊四醇六(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、異氰尿酸三[(甲基)丙烯醯基乙基]酯、聚酯(甲基)丙烯酸酯低聚物等不飽和一元酸及多元醇或多酚之酯；(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、檸康酸酐、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-(2,5-二側氧四氫呋喃基)-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酸之醯胺；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、二乙烯基苯、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、乙烯基苄基甲基醚、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；乙烯基胺、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；烯丙醇、巴豆醇等乙烯醇；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、氯丁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、聚矽氧烷等聚合物分子鏈之末端具有單(甲基)丙烯醯基之巨單體類；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聚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多聚環氧化合物之乙烯基環氧化合物。 [化30]
Figure 02_image071
[化31]
Figure 02_image073
[化32]
Figure 02_image075
[化33]
Figure 02_image077
作為上述乙烯性不飽和化合物(B)，亦可使用市售品，作為市售品，例如可列舉：Kayarad DPHA、DPEA-12、PEG400DA、THE-330、RP-1040、NPGDA、PET30(日本化藥製造)、SPC-1000、SPC-3000(昭和電工製造)、ARONIX M-140、M-215、M-350(東亞合成公司製造)、NK Ester A-DPHA-TMPT、A-DCP、A-HD-N、A-9300、TMPT、DCP、NPG及HD-N(新中村化學工業公司製造)等。 較佳為於該等乙烯性不飽和化合物中的兩末端具有羧基及羥基之聚合物之單(甲基)丙烯酸酯、具有1個羧基及2個以上(甲基)丙烯醯基之多官能(甲基)丙烯酸酯、不飽和一元酸與多元醇或多酚之酯中含有本發明之肟酯化合物的光聚合起始劑。 乙烯性不飽和化合物可單獨使用或將2種以上混合使用，又，於將2種以上混合使用之情形時，亦可預先將該等進行共聚，以共聚物之形式而使用。 可使本發明之感光性組合物進而含有著色劑(C)，而製成著色感光性組合物。作為該著色劑(C)，可列舉顏料、染料、天然色素等。該等著色劑可單獨使用或將2種以上混合使用。 作為上述顏料，例如可使用：亞硝基化合物；硝基化合物；偶氮化合物；重氮化合物；
Figure 107108827-A0304-12-0019-1
Figure 107108827-A0304-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；喹吖酮化合物；蒽締蒽酮化合物；芘化合物；苝化合物；吡咯并吡咯二酮化合物；硫靛藍化合物；二㗁𠯤化合物；三苯甲烷化合物；喹酞酮化合物；萘四羧酸；偶氮染料、花青染料之金屬錯合物；色澱顏料；藉由爐法、導槽法(channel method)或熱方法而獲得之碳黑、或乙炔黑、科琴黑或燈黑等碳黑；利用環氧樹脂製備或被覆上述碳黑而成者、將上述碳黑預先於溶解於溶劑中並於樹脂中進行分散處理使之吸附20～200 mg/g之樹脂而成者、對上述碳黑進行過酸性或鹼性表面處理者、平均粒徑為8 nm以上且DBP(Dibutyl phthalate，鄰苯二甲酸二丁酯)吸油量為90 ml/100 g以下之碳黑、根據950℃下之揮發分中之CO及CO2 所算出之總氧量為每100 m2 表面積9 mg以上之碳黑；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；氧化鉻綠、米洛麗藍、鈷綠、鈷青、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、黃丹、鋅黃、鐵丹(氧化鐵紅(III))、鎘紅、合成鐵黑、棕土等有機或無機顏料。該等顏料可單獨使用或將複數種混合使用。 作為上述顏料，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。 作為上述染料，可列舉：偶氮染料、蒽醌染料、靛屬染料、三芳基甲烷染料、
Figure 107108827-A0304-12-0019-1
Figure 107108827-A0304-xxxx-3
染料、茜素染料、吖啶染料、茋染料、噻唑染料、萘酚染料、喹啉染料、硝基染料、吲達胺染料、㗁𠯤染料、酞菁染料、花青染料等染料等，該等有時單獨使用，亦有時將複數種混合使用。 於本發明之感光性組合物中，上述著色劑(C)之含量相對於上述乙烯性不飽和化合物(B)100質量份較佳為5～100質量份，更佳為10～50質量份。 可使本發明之感光性組合物進而含有鹼性顯影性化合物(D)而製成鹼性顯影性感光性樹脂組合物。同時含有著色劑(C)及鹼性顯影性化合物(D)者亦稱為著色鹼性顯影性感光性樹脂組合物。 作為上述鹼性顯影性化合物(D)，只要為可溶於鹼性水溶液之化合物則並無特別限定，例如可列舉日本專利特開2004-264414號公報記載之樹脂等。 又，作為上述鹼性顯影性化合物(D)，可使用丙烯酸酯之共聚物、或苯酚及/或甲酚酚醛清漆環氧樹脂、具有多官能環氧基之聚苯甲烷型環氧樹脂、環氧丙烯酸酯樹脂、使不飽和一元酸與下述通式(V)所表示之環氧化合物等環氧化合物之環氧基進行作用並進而使多元酸酐與之進行作用所獲得之樹脂。此處所述之所謂環氧丙烯酸酯樹脂，係使(甲基)丙烯酸與上述環氧化合物進行作用而得者，作為其例，可列舉Ripoxy SPC-2000、DIC公司製造之DICLITE UE-777、日本U-PICA公司製造U-PICA 4015等。 該等之中，較佳為使不飽和一元酸與環氧丙烯酸酯樹脂、及下述通式(V)所表示之環氧化合物之環氧基進行作用並進而使多元酸酐與之進行作用所獲得之樹脂。 [化34]
Figure 02_image079
(式中，X6 表示直接鍵、亞甲基、碳原子數1～4之亞烷基、碳原子數3～20之脂環式烴基、-O-、-S-、-SO-2 、-SS-、-SO-、-CO-、-OCO-或下述[化35-1]、[化35-2]或[化35-3]所表示之基，且上述亞烷基有時被取代為鹵素原子，R81 及R82 分別獨立地表示碳原子數1～5之烷基、碳原子數1～8之烷氧基、碳原子數2～5之烯基或鹵素原子，且上述烷基、烷氧基及烯基有時被取代為鹵素原子； R81 及R82 於分別存在複數個之情形時，有時相同亦有時不同； c為0～4之整數； d為0～4之整數； m為0～10之整數； 於m不為0之情形時，存在光學異構物，無論何種異構物均可)。 [化35-1]
Figure 02_image081
(式中，Z3 表示氫原子、有時被取代為碳原子數1～10之烷基或碳原子數1～10之烷氧基之苯基、或有時被取代為碳原子數1～10之烷基或碳原子數1～10之烷氧基之碳原子數3～10之環烷基，Y1 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、烷氧基及烯基有時被取代為鹵素原子，d為0～5之整數)。 [化35-2]
Figure 02_image083
[化35-3]
Figure 02_image085
(式中，Y2 及Z4 分別獨立地表示有時被取代為鹵素原子之碳原子數1～10之烷基、有時被取代為鹵素原子之碳原子數6～20之芳基、有時被取代為鹵素原子之碳原子數6～20之芳氧基、有時被取代為鹵素原子之碳原子數6～20之芳硫基、有時被取代為鹵素原子之碳原子數6～20之芳基烯基、有時被取代為鹵素原子之碳原子數7～20之芳烷基、有時被取代為鹵素原子之碳原子數2～20之雜環基、或鹵素原子，且上述烷基及芳烷基中之伸烷基部分有時被不飽和鍵、-O-或-S-中斷，Z4 有時以鄰接之Z4 彼此形成環，p表示0～4之整數，q表示0～8之整數，r表示0～4之整數，s表示0～4之整數，r與s之數之合計為2～4之整數)。 作為上述使之與環氧化合物進行作用之上述不飽和一元酸，可列舉：丙烯酸、甲基丙烯酸、丁烯酸、桂皮酸、山梨酸、甲基丙烯酸羥基乙酯・順丁烯二酸酯、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、丙烯酸羥基丙酯・順丁烯二酸酯、二環戊二烯・順丁烯二酸酯等。 作為上述使不飽和一元酸進行作用之後使之進行作用之上述多元酸酐，可列舉：聯苯四羧酸二酐、四氫鄰苯二甲酸酐、琥珀酸酐、聯苯四甲酸二酐、順丁烯二酸酐、偏苯三甲酸酐、均苯四甲酸酐、2,2'-3,3'-二苯甲酮四羧酸酐、乙二醇雙脫水偏苯三酸酯、甘油三脫水偏苯三酸酯、六氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、耐地酸酐、甲基耐地酸酐、三烷基四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、5-(2,5-二側氧四氫呋喃基)-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。 上述環氧化合物、上述不飽和一元酸及上述多元酸酐之反應莫耳比較佳為設為如下。 即，於具有相對於上述環氧化合物之1個環氧基加成0.1～1.0個上述不飽和一元酸之羧基之結構的環氧加成物中，較佳為使之成為如下比率：相對於該環氧加成物之1個羥基，上述多元酸酐之酸酐結構成為0.1～1.0個。 上述環氧化合物、上述不飽和一元酸及上述多元酸酐之反應可按照常規方法而進行。 又，鹼性顯影性化合物有時具有乙烯性不飽和鍵。即，上述乙烯性不飽和化合物(B)與上述鹼性顯影性化合物(D)有時為相同之化合物。於此情形時，具有鹼性顯影性且具有乙烯性不飽和鍵之化合物較佳為含有0.2～1.0當量之不飽和基。 再者，於使用具有鹼性顯影性且具有乙烯性不飽和鍵之化合物之情形時，關於該化合物，於算出上述光聚合起始劑(A)之含量及著色劑(C)之含量時，設為包含於乙烯性不飽和化合物(B)中。 於將本發明之感光性組合物製成鹼性顯影性感光性樹脂組合物之情形時，關於有時具有乙烯性不飽和鍵之上述鹼性顯影性化合物(D)之含量，於本發明之鹼性顯影性感光性樹脂組合物中較佳為1～20質量%，尤其是3～12質量%。 為了進行酸值調整而使本發明之(著色)鹼性顯影性感光性樹脂組合物之顯影性改良，可與有時具有乙烯性不飽和鍵之上述鹼性顯影性化合物(D)同時進而使用單官能或多官能環氧化合物。有時具有乙烯性不飽和鍵之上述鹼性顯影性化合物(D)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進行選擇。 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、環氧化亞麻籽油、丁酸縮水甘油酯、一氧化乙烯基環己烷、1,2-環氧-4-乙烯基環己烷、環氧苯乙烷、氧化蒎烯、甲基環氧苯乙烷、環氧環己烷、環氧丙烷、上述化合物No.A2、No.A3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1種以上之化合物，則可獲得特性更良好之(著色)鹼性顯影性感光性樹脂組合物，因而較佳。 作為上述雙酚型環氧化合物，除可使用上述通式(V)所表示之環氧化合物以外，例如亦可使用氫化雙酚型環氧化合物等雙酚型環氧化合物。 又，作為上述縮水甘油醚類，可使用：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)甲烷等。 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-6-甲基環己基甲基-3,4-環氧-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-5,5-二甲尿囊素、三縮水甘油基異氰尿酸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；三苯甲烷型環氧化合物；二環戊二烯型環氧化合物等。 可使本發明之感光性組合物進而含有溶劑。作為該溶劑，通常可列舉視需要可溶解或分散上述各成分(光聚合起始劑(A)及乙烯性不飽和化合物(B)等)之溶劑，例如：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、戊醇等醇系溶劑；乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、丙二醇-1-單甲醚-2-乙酸酯(PGMEA)、二丙二醇單甲醚乙酸酯、3-甲氧基丁醚乙酸酯、乙氧基乙醚丙酸酯等醚酯系溶劑；苯、甲苯、二甲苯等BTX(Benzene-Toluene-Xylene，苯、甲苯、二甲苯)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公司)、Solvesso#100(Exxon Chemical公司)等烷烴系溶劑；四氯化碳、氯仿、三氯乙烯、二氯甲烷、1,2-二氯乙烷等鹵化脂肪族烴系溶劑；氯苯等鹵化芳香族烴系溶劑；卡必醇系溶劑；苯胺；三乙基胺；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(DMAc)；N-甲基吡咯啶酮；二甲基亞碸；水等；該等溶劑可使用1種或作為2種以上之混合溶劑而使用。 該等之中，較佳為酮類、醚酯系溶劑等、尤其是丙二醇-1-單甲醚-2-乙酸酯、環己酮等，其原因在於：於感光性組合物中，抗蝕劑與光聚合起始劑(A)之相溶性較佳。 於本發明之感光性組合物中，溶劑之含量並無特別限定，於感光性組合物總量100質量%中較佳為30～95質量%，更佳為50～95質量%。於溶劑之含量為上述範圍之情形時，成為操作性(感光性組合物之黏度或潤濕性)、乾燥時之不均之減少、及液體穩定性(不伴隨組合物所包含之成分之析出或沈澱)優異之感光性組合物，於獲得硬化物時能夠適當地控制硬化物之厚度，因而較佳。 又，於本發明之感光性組合物可視需要加入對苯甲醚、對苯二酚、鄰苯二酚、第三丁基兒茶酚、無機化合物、潛伏性添加劑、有機聚合物、鏈轉移劑、增感劑、界面活性劑、矽烷偶合劑、三聚氰胺化合物、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；抗氧化劑；紫外線吸收劑；分散劑、分散助劑；撥油墨劑；抗凝聚劑；觸媒；硬化促進劑；交聯劑；增黏劑等慣用之任意添加物。 於本發明之感光性組合物中可加入使著色劑(C)及/或無機化合物分散之分散劑。作為該分散劑，只要為可使著色劑(C)或無機化合物分散、穩定化者，則並無限制，可使用市售之分散劑，例如BYK-Chemie公司製造之BYK series等。特別是可較佳地使用具有鹼性官能基之包含聚酯、聚醚、或聚胺基甲酸酯之高分子分散劑，尤其是該鹼性官能基為胺及/或其四級鹽且胺值為1～100 mgKOH/g者。 上述所謂潛伏性添加劑，係指於常溫下於光曝光步驟及預烤步驟中為惰性且藉由於100～250℃下進行加熱、或於酸/鹼性觸媒存在下於80～200℃下進行加熱，保護基會脫離而活化者。作為藉由活化而獲得之效果，可列舉抗氧化、紫外線吸收、防污性、再塗佈性及密接性等。 作為上述潛伏性添加劑，可較佳地使用國際公開第2014/021023號說明書所記載者。 作為上述潛伏性添加劑之較佳之例，除國際公開第2014/021023號說明書所記載之潛伏性添加劑以外，還可列舉下述通式(A)～(C)所表示者。 [化36]
Figure 02_image087
(式中，環A1 為六員環之脂環、芳香環或雜環； R81 、R82 、R83 、R84 及R85 表示氫原子、鹵素原子、氰基、羥基、硝基、羧基、有時具有取代基之碳原子數1～40之烷基、碳原子數6～20之芳基、碳原子數7～20之芳烷基或碳原子數2～20之含雜環之基、或-O-R86 ，R81 、R82 、R83 、R84 及R85 之中至少1者不為氫原子； R86 表示碳原子數1～20之烷基、碳原子數2～20之烯基、碳原子數6～20之芳基、碳原子數7～20之芳烷基、碳原子數2～20之含雜環之基或三烷基矽烷基)。 [化37]
Figure 02_image089
(式中，環A1 與上述通式(A)相同，R91 與上述通式(A)之R86 相同； X7 為下述通式(1)所表示之基； R92 、R93 、R94 及R95 表示氫原子、鹵素原子、氰基、羥基、硝基、羧基、有時具有取代基之碳原子數1～40之烷基、碳原子數6～20之芳基、碳原子數7～20之芳烷基或碳原子數2～20之含雜環之基，R92 、R93 、R94 及R95 之中至少1者不為氫原子)。 [化38]
Figure 02_image091
(上述通式(1)中，X8 表示-CR97 R98 -、-NR99 -、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之雜環基、或下述[化39][化40-1][化40-2]所示之任一基； 該脂肪族烴基中之亞甲基有時被取代為-O-、-S-、-CO-、-COO-、-OCO-或-NH-、或者於氧原子不相鄰之情況下被取代為將該等組合而成之鍵結基； R97 及R98 表示氫原子、碳原子數1～8之烷基、碳原子數6～20之芳基或碳原子數7～20之芳烷基； Z5 及Z6 分別獨立地表示直接鍵、-O-、-S-、-CO-、-CO-O-、-O-CO-、-SO2 -、-SS-、-SO-或-NR100 -； R99 及R100 表示氫原子、有時具有取代基之碳原子數1～35之脂肪族烴基、有時具有取代基之碳原子數6～35之芳香族烴基或有時具有取代基之碳原子數2～35之雜環基； *表示鍵結鍵)。 [化39]
Figure 02_image093
(上述式中，R101 表示氫原子、有時具有取代基之苯基或碳原子數3～10之環烷基，R102 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、烷氧基及烯基有時具有取代基，f為0～5之整數，*表示鍵結鍵)。 [化40-1]
Figure 02_image095
(式中，*表示鍵結鍵)。 [化40-2]
Figure 02_image097
(上述式中，R103 及R104 分別獨立地表示有時具有取代基之碳原子數1～10之烷基、有時具有取代基之碳原子數6～20之芳基、有時具有取代基之碳原子數6～20之芳氧基、有時具有取代基之碳原子數6～20之芳硫基、有時具有取代基之碳原子數6～20之芳基烯基、有時具有取代基之碳原子數7～20之芳烷基、有時具有取代基之碳原子數2～20之雜環基或鹵素原子，該烷基及芳烷基中之亞甲基有時被不飽和鍵、-O-或-S-中斷，R103 有時以鄰接之R103 彼此形成環，b表示0～4之數，c表示0～8之數，g表示0～4之數，h表示0～4之數，g與h之數之合計為2～4)。 [化41]
Figure 02_image099
(式中，k＝2～6，X9 為k＝2時上述通式(1)所表示之基、k＝3時下述通式(2)所表示之基、k＝4時下述通式(3)所表示之基、k＝5時下述通式(4)、k＝6時下述通式(5)； R111 、R112 、R113 及R114 表示氫原子、鹵素原子、氰基、羥基、硝基、羧基、或有時具有取代基之碳原子數1～40之烷基、碳原子數6～20之芳基、碳原子數7～20之芳烷基或碳原子數2～20之含雜環之基，R111 、R112 、R113 及R114 之中至少1者不為氫原子； 環A1 及R86 與上述通式(A)相同)。 [化42]
Figure 02_image101
(上述通式(2)中，Y11 表示三價之碳原子數1～35之脂肪族烴基、碳原子數3～35之脂環式烴基、碳原子數6～35之芳香族烴基或碳原子數2～35之雜環基； Z11 、Z12 及Z13 分別獨立地表示直接鍵、-O-、-S-、-CO-、-CO-O-、-O-CO-、-SO2 -、-SS-、-SO-、-NR121 -、-PR121 -、有時具有取代基之碳原子數1～35之脂肪族烴基、有時具有取代基之碳原子數6～35之芳香族烴基、或有時具有取代基之碳原子數2～35之雜環基； R121 表示氫原子、有時具有取代基之碳原子數1～35之脂肪族烴基、有時具有取代基之碳原子數6～35之芳香族烴基或有時具有取代基之碳原子數2～35之雜環基，該脂肪族烴基中之亞甲基有時被取代為碳-碳雙鍵、-O-、-CO-、-O-CO-、-CO-O-或-SO2 -)。 [化43]
Figure 02_image103
(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之雜環基； 該脂肪族烴基中之亞甲基有時被取代為-COO-、-O-、-OCO-、-NHCO-、-NH-或-CONH-； Z11 ～Z14 分別獨立，為與上述通式(2)之Z11 ～Z13 所表示之基相同之範圍之基)。 [化44]
Figure 02_image105
(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6～30之芳香族烴基或碳原子數2～30之雜環基； 該脂肪族烴基有時被-COO-、-O-、-OCO-、-NHCO-、-NH-或-CONH-中斷； Z11 ～Z15 分別獨立，為與上述通式(2)之Z11 ～Z13 所表示之基相同之範圍之基)。 [化45]
Figure 02_image107
(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之雜環基； 該脂肪族烴基有時被-COO-、-O-、-OCO-、-NHCO-、-NH-或-CONH-中斷； Z11 ～Z16 分別獨立，為與上述通式(2)之Z11 ～Z13 所表示之基相同之範圍之基)。 又，藉由使用上述有機聚合物(除乙烯性不飽和化合物(B)及鹼性顯影性化合物(D)以外)，亦可改善硬化物之特性。作為該有機聚合物，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(acrylonitrile-butadiene-styrene，丙烯-丁二烯-苯乙烯)樹脂、尼龍6、尼龍66、尼龍12、胺基甲酸酯樹脂、聚碳酸酯聚乙烯醇縮丁醛、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，該等之中，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。 於使用有機聚合物之情形時，其使用量相對於乙烯性不飽和化合物(B)100質量份較佳為10～500質量份。 作為上述鏈轉移劑或上述增感劑，一般使用含硫原子化合物。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-巰基菸鹼酸、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、使該巰基化合物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、丁二醇雙硫代丙酸酯、丁二醇雙硫代乙醇酸酯、乙二醇雙硫代乙醇酸酯、三羥甲基丙烷三硫代乙醇酸酯、丁二醇雙硫代丙酸酯、三羥甲基丙烷三硫代丙酸酯、三羥甲基丙烷三硫代乙醇酸酯、季戊四醇四硫代丙酸酯、季戊四醇四硫代乙醇酸酯、三羥基乙基三硫代丙酸酯、二乙基9-氧硫
Figure 107108827-A0304-12-0019-1
Figure 107108827-A0304-xxxx-3
、二異丙基9-氧硫
Figure 107108827-A0304-12-0019-1
Figure 107108827-A0304-xxxx-3
、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46]
Figure 02_image109
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系界面活性劑；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、山梨糖醇酐脂肪酸酯、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，該等單獨使用或組合使用均可。 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，其中可較佳地使用KBE-9007、KBM-502、KBE-403等具有異氰酸基、甲基丙烯醯基或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)羥甲基苯并胍胺、(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等。 此處，作為構成烷基醚之烷基，可列舉甲基、乙基或丁基，有時相互相同亦有時不同。又，未經烷基醚化之羥甲基有時於一分子內自縮合，且有時於兩個分子間進行縮合而導致形成低聚物成分。 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。該等之中，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。 作為上述調平劑，只要為具有調平效果者則並無特別限定，可使用既有之調平劑，其中可尤佳地使用聚矽氧系調平劑及氟系調平劑。 作為上述聚矽氧系調平劑，可使用市售之聚矽氧系調平劑，例如可使用BYK-300、BYK-306、BYK-307、BYK-310、BYK-315、BYK-313、BYK-320、BYK-322、BYK-323、BYK-325、BYK-330、BYK-331、BYK-333、BYK-337、BYK-341、BYK-344、BYK-347、BYK-348、BYK-349、BYK-370、BYK-375、BYK-377、BYK-378、BYK-UV3500、BYK-UV3510、BYK-UV3570、BYK-3550、BYK-SILCLEAN3700、BYK-SILCLEAN3720(以上，BYK-Chemie Japan製造)；ACFS 180、AC FS 360、AC S20(以上，Algin Chemie製造)；Polyflow KL-400X、Polyflow KL-400HF、Polyflow KL-401、Polyflow KL-402、Polyflow KL-403、Polyflow KL-404(以上，共榮社化學製造)；KP-323、KP-326、KP-341、KP-104、KP-110、KP-112(以上，信越化學工業製造)；LP-7001、LP-7002、8032 ADDITIVE、57 ADDITIVE、L-7604、FZ-2110、FZ-2105、67ADDITIVE、8618 ADDITIVE、3ADDITIVE、56 ADDITIVE(以上，Dow Corning Toray製造)等市售品。 作為上述氟系調平劑，可使用市售之氟系調平劑，例如使用OPTOOL DSX、OPTOOL DAC-HP(以上，DAIKIN INDUSTRIES製造)；Surflon S-242、Surflon S-243、Surflon S-420、Surflon S-611、Surflon S-651、Surflon S-386(以上，AGC Seimi Chemical製造)；BYK-340(BYK-Chemie Japan製造)；AC110a、AC 100a(以上，Algin Chemie製造)；MEGAFAC F-114、MEGAFAC F-410、MEGAFAC F-444、MEGAFAC EXPTP-2066、MEGAFAC F-430、MEGAFAC F-472SF、MEGAFAC F-477、MEGAFAC F-552、MEGAFAC F-553、MEGAFAC F-554、MEGAFAC F-555、MEGAFAC R-94、MEGAFAC RS-72-K、MEGAFAC RS-75、MEGAFAC F-556、MEGAFAC EXPTF-1367、MEGAFAC EXP TF-1437、MEGAFAC F-558、MEGAFAC EXPTF-1537(以上，DIC製造)；FC-4430、FC-4432(以上，Sumitomo 3M製造)；FTERGENT 100、FTERGENT 100C、FTERGENT 110、FTERGENT 150、FTERGENT 150CH、FTERGENT A-K、FTERGENT 501、FTERGENT 250、FTERGENT 251、FTERGENT 222F、FTERGENT 208G、FTERGENT 300、FTERGENT 310、FTERGENT 400SW(以上，NEOS製造)；PF-136A、PF-156A、PF-151N、PF-636、PF-6320、PF-656、PF-6520」、PF-651、PF-652、PF-3320(以上，北村化學產業製造)等市售品。 於本發明之感光性組合物中，除光聚合起始劑(A)、乙烯性不飽和化合物(B)、著色劑(C)、鹼性顯影性化合物(D)、溶劑及有機聚合物以外，任意添加物之使用量可視其使用目的而適當選擇，並無特別限制，較佳為相對於上述乙烯性不飽和化合物(B)100質量份，合計設為50質量份以下。 本發明之感光性組合物、鹼性顯影性感光性樹脂組合物或硬化物可較佳地用於顯示器顯示裝置，詳細而言，可較佳地用於顯示器顯示裝置(彩色電視、PC(Pesonal Computer，個人電腦)顯示器、攜帶型資訊終端、數位相機等)之彩色顯示之液晶顯示元件中之彩色濾光片。除此以外，還可用於光硬化性塗料或清漆；光硬化性接著劑；印刷基板；CCD(Charge Coupled Device，電荷耦合元件)影像感測器之彩色濾光片；電漿顯示面板用之電極材料；粉末塗層；印刷油墨；印刷版；接著劑；牙科用組合物；凝膠塗層；電子學用之光阻；電鍍阻劑；蝕刻阻劑；乾膜；阻焊劑；用以形成各種顯示器顯示裝置之構造之抗蝕劑；用以封入電氣及電子零件之組合物；防焊劑；磁性記錄材料；微型機械零件；波導；光開關；鍍覆用遮罩；蝕刻遮罩；色彩試驗系統；玻璃纖維電纜塗層；網版印刷用模板；用以藉由立體光刻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；用以圖像記錄材料之脫色材料；使用微膠囊之圖像記錄材料用之脫色材料；印刷配線板用光阻材料；UV(ultraviolet，紫外線)及可見光雷射直接圖像系統用之光阻材料；印刷電路基板之逐次積層中之介電層形成所使用之光阻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或鹼性顯影性感光性樹脂組合物亦可以形成液晶顯示面板用之間隔物為目的及以形成垂直配向型液晶顯示元件用突起為目的而使用。尤其是作為用以同時形成垂直配向型液晶顯示元件用之突起及間隔物之感光性組合物有用。 關於使用本發明之感光性組合物或鹼性顯影性感光性樹脂組合物製造硬化物之方法，於下文詳細地進行說明。 本發明之感光性組合物或鹼性顯影性感光性樹脂組合物可藉由照射能量線而使之硬化。 本發明之感光性組合物或鹼性顯影性感光性樹脂組合物可於硬化之前利用旋轉塗佈機、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、浸漬等公知之方法應用於鈉玻璃、石英玻璃、半導體基板、金屬、紙、塑膠等支持基體上。又，亦可於暫時施加於膜等支持基體上之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鹼性顯影性感光性樹脂組合物硬化時所使用之能量線，可利用自超高壓水銀燈、高壓水銀燈、中壓水銀燈、低壓水銀燈、水銀蒸汽電弧燈、氙弧燈、碳弧燈、金屬鹵素燈、螢光燈、鎢絲燈、準分子燈、殺菌燈、發光二極體、CRT(Cathode-Ray Tube，陰極射線管)光源等光源所獲得之具有2000埃至7000埃之波長之電磁波能量線、或電子束、X射線、放射線等高能量線，較佳為使用發出波長300～450 nm之光之超高壓水銀燈、水銀蒸汽電弧燈、碳弧燈、氙弧燈等光源。 進而，就不僅可謀求生產性之提昇，亦可謀求解像性或位置精度等之提昇之方面而言，有用的是藉由曝光光源使用雷射光，不使用遮罩而根據電腦等之數位資訊直接形成圖像之雷射直接刻寫法，作為其雷射光，可較佳地使用340～430 nm之波長之光，亦可使用準分子雷射、氮氣雷射、氬離子雷射、氦-鎘雷射、氦-氖雷射、氪離子雷射、各種半導體雷射及YAG(Yttrium Aluminum Garnet，釔-鋁-石榴石)雷射等發出可見光至紅外光之區域之光者。於使用該等雷射之情形時，可加入吸收可見光至紅外光之該區域之光的增感色素。 又，上述液晶顯示面板用間隔物可藉由如下步驟較佳地形成：(1)於基板上形成本發明之感光性組合物之塗膜；(2)經由具有特定之圖案形狀之遮罩對該塗膜照射放射線；(3)曝光後之烘烤；(4)使曝光後之該覆膜進行顯影；及(5)對顯影後之該覆膜進行加熱。 又，本發明之感光性組合物於含有撥油墨劑之情形時作為噴墨方式用間隔壁形成樹脂組合物有用，該組合物可作為彩色濾光片用而使用，尤其是可較佳地用於齒形角為50°以上之噴墨方式彩色濾光片用間隔壁。作為該撥油墨劑，可較佳地使用氟系界面活性劑及包含氟系界面活性劑之組合物。 於將本發明之感光性組合物製成含有撥油墨劑者並用作上述噴墨方式用間隔壁形成樹脂組合物之情形時，可藉由如下方法製造光學元件：由本發明之感光性組合物所形成之間隔壁於被轉印體上進行劃分，藉由噴墨法對經劃分之被轉印體上之凹部賦予液滴而形成圖像區域。此時，較佳為上述液滴含有著色劑而使上述圖像區域著色，藉此可獲得基板上至少具有包含複數個著色區域之像素群及將上述像素群之各著色區域隔離之間隔壁的光學元件。 [實施例] 以下，列舉實施例及比較例對本發明進一步詳細地進行說明，但本發明並不受該等實施例等所限定。 [實施例1]化合物No.1之製造 (步驟1)中間物1A(鹵化芳基化合物)之製造 分別稱量2-氯-4'-氟苯乙酮(3.59 g)、水楊酸醛(5.08 g)、碳酸鉀(5.75 g)、及丙酮(15 g)至100 ml之四口燒瓶中後，進行加熱回流1小時。冷卻至室溫之後，添加離子交換水(41.6 g)，濾取析出物並使之充分地乾燥，獲得作為淡黃色固體之中間物1A(4.74 g：產率95%)。 [化47]
Figure 02_image111
(步驟2)中間物1B(酮化合物)之製造 分別稱量中間物1A(4.42 g)、下述吲哚化合物1A(4.07 g)、碳酸鉀(4.62 g)及DMAc(23.25 g)至100 ml之四口燒瓶中後，於110℃下進行3小時反應。加入離子交換水(15.5 g)及乙酸乙酯(23.25 g)，進行油水分離，將有機層水洗3次而進行脫溶劑。其後，對所獲得之殘渣加入乙酸乙酯(15.5 g)及己烷(23.25 g)，進行加熱溶解後進行冷卻而進行再結晶。冷卻至5℃之後，濾取析出物並使之充分地乾燥，獲得作為白色固體之中間物1B(6.8 g：產率87%)。 [化48]
Figure 02_image113
[化49]
Figure 02_image115
(步驟3)中間物1C(肟化合物)之製造 稱量中間物1B(3.74 g)及DMF(12.93 g)至30 ml之二口燒瓶中，於5℃下一面攪拌一面滴加35%鹽酸1.26 g及亞硝酸異丁酯0.87 g，並於室溫下攪拌30小時。加入離子交換水(11.9 g)及乙酸乙酯(11.9 g)進行油水分離，並將有機層水洗3次。使有機層脫溶劑後，藉由二氧化矽凝膠管柱(乙酸乙酯/己烷＝1/9)進行精製，獲得作為淡黃色固體之中間物1C(3.0 g：產率75%)。 [化50]
Figure 02_image117
(步驟4)化合物No.1(本發明之肟酯化合物)之製造 分別稱量中間物1C(2.21 g)及THF(7.2 g)至30 ml之2口圓底燒瓶中，於氮氣流、冰浴冷卻下滴加乙醯氯(2.12 g)、三乙基胺(2.72 g)，並於室溫下攪拌1小時。加入離子交換水(7.2 g)及乙酸乙酯(7.2 g)進行油水分離，並將有機層水洗3次。使有機層脫溶劑後，藉由二氧化矽凝膠管柱(乙酸乙酯/己烷)進行精製，獲得作為淡黃色固體之化合物No.1(1.5 g：產率63%)。 將所獲得之化合物No.1之分析結果示於[表1]～[表3]。再者，於[表1]中一併記載之OXE 02為後述比較例1所使用之市售之光聚合起始劑。 [化51]
Figure 02_image119
[實施例2]化合物No.189之製造 (步驟1)中間物2A之製造 添加9.6 g上述中間物1B、二甲基乙醯胺30.0 g、鹽酸羥胺2.2 g，其後，於60℃下添加氫氧化鈉1.2 g。使之於60℃下反應2小時，其後，添加離子交換水、氯仿，一面加溫一進進行萃取。將有機層水洗3次，脫溶劑後藉由二氧化矽凝膠管柱(乙酸乙酯/己烷＝1/6)進行精製，獲得下述中間物2A(2.0 g：產率25%)。 [化52]
Figure 02_image121
(步驟2)化合物No.189(本發明之肟酯化合物)之製造 將中間物1C變更為上述中間物2A，除此以外，以與實施例1之步驟4相同之方式獲得化合物No.189。 [實施例3]化合物No.190之製造 (步驟1)中間物3B之製造 將吲哚化合物1A變更為下述咔唑化合物3A，除此以外，以與實施例1之步驟2相同之方式獲得下述中間物3B。 [化53]
Figure 02_image123
(步驟2)中間物3C之製造 於100 ml之四口燒瓶中添加氯化鋁2.72 g、二氯乙烷30.0 g，於冰浴冷卻下添加7.54 g中間物3B，繼而，添加辛醯氯3.32 g。使之於室溫下反應1小時，其後，將反應液倒出至冰水中進行油水分離。將有機層水洗3次之後，進行脫溶劑，藉由二氧化矽凝膠管柱(乙酸乙酯/己烷＝1/10)獲得下述中間物3C(1.1 g：產率11%)。 [化54]
Figure 02_image125
(步驟3)No.190之製造 將中間物1C變更為上述中間物3C，除此以外，以與實施例1之步驟4相同之方式獲得上述化合物No.190。 [實施例4]化合物No.191之製造 將實施例1之步驟2中所使用之中間物1A變更為下述中間物4A，除此以外，以與實施例1相同之方式獲得上述化合物No.191。 [化55]
Figure 02_image127
[實施例5]化合物No.192之製造 將實施例1之步驟2中所使用之中間物1A變更為下述中間物5A，除此以外，以與實施例1相同之方式獲得上述化合物No.192。 [化56]
Figure 02_image129
[實施例6]化合物No.193之製造 (步驟1)中間物6B之製造 將吲哚化合物1A變更為下述啡噻𠯤化合物6A，除此以外，以與實施例1之步驟2相同之方式獲得下述中間物6B。 [化57]
Figure 02_image131
(步驟2)中間物6C之製造 將中間物3B變更為上述中間物6B，並以所使用之試劑之當量成為2倍量之方式進行製備，除此以外，以與實施例3之步驟2相同之方式獲得下述中間物6C。 [化58]
Figure 02_image133
(步驟3)中間物6D之製造 將中間物1B變更為上述中間物6C，並以所使用之試劑之當量成為2倍量之方式進行製備，除此以外，以與實施例1之步驟3相同之方式獲得下述中間物6D。 [化59]
Figure 02_image135
(步驟4)化合物No.193之製造 將中間物1C變更為上述中間物6D，並以所使用之試劑之當量成為2倍量之方式進行製備，除此以外，以與實施例1之步驟4相同之方式獲得上述化合物No.193。 [實施例7]化合物No.194之製造 (步驟1)中間物7A之製造 將中間物1B變更為上述中間物6C，除此以外，以與實施例1之步驟3相同之方式獲得下述中間物7A。 [化60]
Figure 02_image137
(步驟2)]化合物No.194之製造 將中間物1C變更為上述中間物7A，除此以外，以與實施例1之步驟4相同之方式獲得上述化合物No.194。 將所獲得之化合物No.189～194之分析結果示於[表1]～[表3]。 [表1]
Figure 107108827-A0304-0001
 [表2]
Figure 107108827-A0304-0002
 [表3]
Figure 107108827-A0304-0003
 如根據上述[表1]所明瞭，本發明之肟酯化合物於以PGMEA為代表之溶劑中之溶解度較高，因此有用。 [製造例1]藍色顏料分散液No.1之製造 使用珠磨機使作為分散劑之DISPERBYK-161(12.5質量份；BYK-Chemie Japan製造)及作為著色劑之顏料藍15：6(15質量份)分散於PGMEA(72.5質量份)中，製造藍色顏料分散液No.1。 [實施例8～14及比較例1]感光性組合物之製備 根據下述[表4]之組成將各成分混合，獲得感光性組合物No.1～No.7(實施例8～14)及比較用之感光性組合物No.8(比較例1)。再者，表中之數字表示質量份。於實施例8～14及比較例1中，分別單獨使用光聚合起始劑。 又，表中之符號表示下述成分。 A-1：化合物No.1(實施例1所獲得之本發明之光聚合起始劑) A-2：化合物No.189(實施例2所獲得之本發明之光聚合起始劑) A-3：化合物No.190(實施例3所獲得之本發明之光聚合起始劑) A-4：化合物No.191(實施例4所獲得之本發明之光聚合起始劑) A-5：化合物No.192(實施例5所獲得之本發明之光聚合起始劑) A-6：化合物No.193(實施例6所獲得之本發明之光聚合起始劑) A-7：化合物No.194(實施例7所獲得之本發明之光聚合起始劑) A-8：OXE 02(不屬於本發明之光聚合起始劑；BASF公司製造) B-1：SPC-3000(具有酸基之乙烯性不飽和化合物；昭和電工製造；固形物成分42.2質量%之PGMEA溶液) B-2：Kayarad DPHA(乙烯性不飽和化合物；日本化藥製造；固形物成分100質量%) C-1：藍色顏料分散液No.1(製造例1所獲得之分散液) X-1：KBE-403(矽烷偶合劑；信越化學製造) X-2：F-554(氟系調平劑、含有含氟基、親油性基之低聚物；DIC製造) Y-1：PGMEA(溶劑) 再者，SPC-3000(B-1)為具有乙烯性不飽和鍵且具有鹼性顯影性之化合物，Kayarad DPHA(B-2)為具有乙烯性不飽和鍵之化合物但不具有鹼性顯影性。 ＜感光性組合物及硬化物之評價＞ 按照下述順序進行感光性組合物No.1～No.7及比較用之感光性組合物No.8之感度以及利用該等所獲得之硬化物之亮度的評價。將評價結果一併記載於[表4]。 (感度) 於玻璃基板上旋轉塗佈(於500 rpm下2秒鐘，繼而，於900 rpm下5秒鐘)感光性組合物No.1～No.7(實施例8～14)及比較用之感光性組合物No.8(比較例1)，並使用加熱板於90℃下進行預烤90秒鐘，其後，於23℃下冷卻40秒鐘。其後，使用高壓水銀燈經由遮罩(遮罩開口30 μm)進行曝光(曝光量40 mJ/cm2 )。使用2.5質量%碳酸鈉水溶液作為顯影液進行顯影，其後，仔細進行水洗，並使用烘箱於230℃下進行後烘烤30分鐘，使圖案固定。對所獲得之圖案利用電子顯微鏡進行觀察，測定與遮罩開口對應之部分之線寬。將線寬為30 μm以上者設為A，將未達30 μm者設為B。線寬越大，意味著感度越良好。 (亮度) 於玻璃基板上旋轉塗佈(於500 rpm下2秒鐘，繼而，於900 rpm下5秒鐘)感光性組合物No.1～No.7(實施例8～14)及比較用之感光性組合物No.8(比較例1)，並使用加熱板於90℃下進行預烤90秒鐘，其後，於23℃下冷卻40秒鐘。其後，使用高壓水銀燈以100 mJ/cm2 進行曝光，而製作評價樣品。根據所獲得之樣品於380～780 nm之透過率，並依據JIS Z8701求出Y值。Y值越高，亮度越高，意味著於可見光區域中具有越高之透過率，從而有用。 [表4]
Figure 107108827-A0304-0004
 根據上述[表4]，明瞭：本發明之肟酯化合物與比較例1所使用之化合物比較，感度較高，又，本發明之硬化物之亮度較高。 根據以上內容，由於使用本發明之肟酯化合物之感光性組合物之光微影性優異，且所獲得之硬化物之亮度優異，因此可知本發明之肟酯化合物為作為光聚合起始劑有用者。 [產業上之可利用性] 本發明之肟酯化合物為可對365 nm(i線)等之明線高效率地產生自由基之高感度者，能夠提供顯影性優異之鹼性顯影性感光性樹脂組合物，又，於有機溶劑中之溶解性亦較高，進而可見光區域之透過率亦較高，作為用於感光性組合物之光聚合起始劑有用。Hereinafter, the photopolymerization initiator of this invention containing the oxime ester compound of this invention and this compound is demonstrated in detail based on preferable embodiment. The oxime ester compound of the present invention is a novel compound represented by the above general formula (Iα) or (Iβ). The oxime ester compound has geometric isomers produced by the double bond of the oxime, but the present invention does not distinguish between them. That is, in this specification, the compound represented by the above-mentioned general formula (Iα) or (Iβ) and its exemplified compounds represent one or more mixtures of these geometric isomers, and are not limited to those with the shown structures. Specific isomers. The hydrocarbon groups having 1 to 20 carbon atoms represented by R 21 to R 24 in the above general formula (Iα) and R 121 to R 124 in the above general formula (Iβ) are not particularly limited, and preferably represent carbon atoms Alkyl group with 1 to 20 carbon atoms, alkenyl group with 2 to 20 carbon atoms, cycloalkyl group with 3 to 20 carbon atoms, cycloalkylalkyl group with 4 to 20 carbon atoms, aromatic group with 6 to 20 carbon atoms group and aralkyl group with 7 to 20 carbon atoms, etc. Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, pentyl, iso Pentyl, tertiary pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, isononyl, decyl, isodecyl, undecyl, Dodecyl, tetradecyl, hexadecyl, octadecyl and eicosyl, etc. Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, ethylene, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, and 3-pentenyl. , 2-hexenyl, 3-hexenyl, 5-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4 -decenyl, 3-undecenyl, 4-dodecenyl, 4,8,12-tetradecatrien-1-ylallyl, etc. The aforementioned cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. Examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentacyclopentadiene Alkenes and bicyclo[1.1.1]pentyl, etc. The above-mentioned cycloalkylalkyl having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which the hydrogen atoms of the alkyl group are substituted by a cycloalkyl group. Examples include: cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, 2-cyclononyl Ethyl, 2-cyclodecylethyl, 3-3-adamantylpropyl and decahydronaphthylpropyl, etc. Examples of the above-mentioned aryl group having 6 to 20 carbon atoms include: phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthracenyl, phenanthrenyl, and benzene substituted with one or more of the above-mentioned alkyl groups. base, biphenyl, naphthyl, anthracenyl, etc. The above-mentioned aralkyl group having 7 to 20 carbon atoms means a group having 7 to 20 carbon atoms in which hydrogen atoms of the alkyl group are substituted by aryl groups. For example, benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, phenylethyl group, naphthylpropyl group, etc. are mentioned. Among the above-mentioned hydrocarbon groups having 1 to 20 carbon atoms, an alkyl group having 1 to 12 carbon atoms and an alkenyl group having 2 to 10 carbon atoms are particularly preferable in terms of sensitivity as a photopolymerization initiator. , Cycloalkyl groups with 3 to 10 carbon atoms, cycloalkylalkyl groups with 4 to 15 carbon atoms, aryl groups with 6 to 15 carbon atoms, and aralkyl groups with 7 to 15 carbon atoms. Examples of heterocyclic ring-containing groups having 2 to 20 carbon atoms represented by R 21 to R 23 in the general formula (Iα) and R 121 to R 123 in the general formula (Iβ) include, for example, pyrrole Base, pyridyl, pyridylethyl, pyrimidyl, pyridyl, piperyl, piperidyl, pyranyl, pyranylethyl, pyrazolyl, trisyl, trisylmethyl, pyrrole Pyridyl, quinolinyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl (furyl), furanyl (furanyl), benzofuranyl (benzofuranyl), thienyl (thienyl), Thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 𠮻rolidinyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinone-1-yl, 2-piperidinone-1-yl, 2,4-dioxyimidazolidin-3-yl and 2 , 4-Dioxyoxazolidine-3-yl, etc. Among the above-mentioned heterocyclic ring-containing groups having 2 to 20 carbon atoms, the heterocyclic ring-containing groups having 2 to 10 carbon atoms are particularly preferred because the photopolymerization initiator has better sensitivity. The methylene group in the group represented by R 21 to R 23 in the above general formula (Iα) may be substituted with -O-, -CO-, -COO-, -OCO-, -NR 24 -, -NR 24 CO-, -S-, -CS-, -SO 2 -, -SCO-, -COS-, -OCS-, or CSO-, and those represented by R 121 to R 123 in the above general formula (Iβ) The methylene group in the group is sometimes substituted by -O-, -CO-, -COO-, -OCO-, -NR 124 -, -NR 124 CO-, -S-, -CS-, -SO 2 - , -SCO-, -COS-, -OCS- or CSO-, these substitutions are carried out by using one or more than two kinds of groups. Under the condition of ortho, it is continuously substituted by two or more groups. As R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , R 9 and R 10 , R 10 and R 11 , R 11 and R 1 , R 101 and R 102 , R 102 and R 103 , R 103 and R 104 , R 105 and R 106 , R 106 and R 107 , R 107 and R 108 , R 108 and R 109 , R 109 and R 110 , R 110 and R 111 , R 111 and R 112 , R 112 and R 113 and R 113 and R 101 are bonded rings, for example, cyclopentane, cyclohexane , cyclopentene, benzene, pyrrolidine, pyrrole, piperone, morpholine, thiomorpholine, tetrahydropyridine, lactone ring and lactamide ring and other 5-7-membered rings, and condensed rings such as naphthalene and anthracene, etc. Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R 31 to R 33 in the above general formula (II) include those same as those of R 21 to R 24 in the above general formula (Iα) or the above general formula (Iβ). The hydrocarbon groups having 1 to 20 carbon atoms represented by R 121 to R 124 are the same. Examples of the heterocyclic ring-containing groups having 2 to 20 carbon atoms represented by R 31 and R 32 in the above general formula (II) include those of R 21 to R 23 in the above general formula (Iα) and the above general formula The heterocyclic ring-containing groups having 2 to 20 carbon atoms represented by R 121 to R 123 in (Iβ) are the same. The methylene group in the group represented by R 31 and R 32 in the above general formula (II) may be substituted with -O-, -CO-, -COO-, -OCO-, -NR 33 -, -NR 33 CO-, -S-, -CS-, -SO 2 -, -SCO-, -COS-, -OCS- or CSO-, the substitution is carried out by using one or more groups, and it can be used continuously In the case of a substituted group, it may be continuously substituted with two or more groups on the condition that the oxygen atoms are not adjacent to each other. Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R 51 to R 54 in the above general formulas (IIIα) and (IIIβ) include those same as those of R 21 to R 24 in the above general formula (Iα) and the above general formula The hydrocarbon groups having 1 to 20 carbon atoms represented by R 121 to R 124 in (Iβ) are the same. Examples of the heterocyclic ring-containing groups having 2 to 20 carbon atoms represented by R 51 to R 53 in the above general formulas (IIIα) and (IIIβ) include the same groups as R 21 to R 23 in the above general formula (Iα). It is the same as the heterocyclic ring-containing group having 2 to 20 carbon atoms represented by R 121 to R 123 in the above general formula (Iβ). Examples of the halogen atom in the above general formulas (Iα), (Iβ), (II), (IIIα) and (IIIβ) include fluorine, chlorine, bromine and iodine. Among the oxime ester compounds of the present invention, the oxime ester compound in which at least one of R3 and R5 in the general formula (Iα) is a group represented by the general formula (II) has a good yield during synthesis and is also easy to purify In terms of better. Also, among the oxime ester compounds of the present invention, the oxime ester compound in which at least one of R 103 and R 106 in the general formula (Iβ) is a group represented by the general formula (II) has a good yield and is easy to synthesize. It is preferable in terms of refining. From the same viewpoint, an oxime ester compound in which both R 103 and R 106 in the general formula (Iβ) are groups represented by the general formula (II) is also preferred. In the above general formulas (Iα) and (Iβ), when R 1 and R 101 are groups or atoms other than those represented by the general formula (II), R 1 and R 101 are hydrogen atoms or cyano groups , especially a hydrogen atom is preferable because it is easy to synthesize. Each of R 2 to R 5 and R 102 to R 107 is also the same as R 1 . That is, when R 2 to R 5 and R 102 to R 106 are groups or atoms other than those represented by general formula (II), if R 2 to R 5 and R 102 to R 106 are hydrogen atoms or A cyano group, especially a hydrogen atom, is preferable because it is easy to synthesize. In addition, in the above general formulas (Iα) and (Iβ), when R 6 and R 108 are groups or atoms other than those represented by the general formula (II), R 6 and R 108 are hydrogen atoms It is preferable because it is easy to synthesize. Among the oxime ester compounds of the present invention, X in the general formula (Iα) does not exist and R and R are bonded to form an oxime ester compound of a benzene ring, which can efficiently absorb near-ultraviolet light (especially 365 nm ) is preferable. Furthermore, in this specification, "X 1 does not exist" means that the bond represented by -X 1 - does not exist in the general formula (Iα) and the state in which a condensed ring skeleton including an N atom and X 1 is not formed . For example, the above " X1 does not exist and R5 and R6 are bonded to form an oxime ester compound of a benzene ring" is a compound having a triphenylamine skeleton rather than a condensed ring skeleton containing an N atom and X1 . As a specific example of the compound For example, the following compound Nos. 153-170 are mentioned. Also, "X 101 does not exist" in the general formula (Iβ) means a state in which a bond represented by -X 101 - does not exist and a condensed ring skeleton including an N atom and X 101 is not formed. In the above general formula (II), R 31 is preferably an alkyl group having 1 to 12 carbon atoms, because the solubility in organic solvents is relatively high. Also, since the reactivity becomes higher, in the above-mentioned general formula (II), R32 is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group, or a phenyl group, and more preferably a phenyl group having 1 carbon atom. -4 alkyl, especially methyl. In the oxime ester compound of the present invention represented by the above-mentioned general formula (Iα), it is preferable that R 9 is a group represented by the above-mentioned general formula (IIIα). Also, in the oxime ester compound of the present invention represented by the above-mentioned general formula (Iα), it is preferable that R 9 is a group represented by the above-mentioned general formula (IIIβ). In the oxime ester compound of the present invention represented by the above-mentioned general formula (Iβ), it is preferable that R 111 is a group represented by the above-mentioned general formula (IIIα). Also, in the oxime ester compound of the present invention represented by the above-mentioned general formula (Iβ), it is preferable that R 111 is a group represented by the above-mentioned general formula (IIIβ). X 2 in the group represented by the above general formula (IIIα) is preferably an oxygen atom or a sulfur atom, especially an oxygen atom. The reason for this is that the oxime ester compound efficiently absorbs long-wavelength near-ultraviolet light and has high sensitivity as a photopolymerization initiator. R 41 to R 45 in the group represented by the above general formula (IIIα) are preferably hydrogen atoms. X 3 in the group represented by the above general formula (IIIβ) is preferably an oxygen atom or a sulfur atom. The reason for this is that the oxime ester compound efficiently absorbs long-wavelength near-ultraviolet light and has high sensitivity as a photopolymerization initiator. R 46 to R 50 in the group represented by the above general formula (IIIβ) are preferably hydrogen atoms. In the oxime ester compound of the present invention represented by the above general formula (Iα), it is preferred that X 1 does not exist. In the oxime ester compound of the present invention represented by the above-mentioned general formula (Iβ), it is preferable that X 101 does not exist, and it is also preferable that X 101 is sulfur. Preferable specific examples of the oxime ester compound of the present invention represented by the above general formula (Iα) or (Iβ) include the following compounds No.1 to No.194. However, the present invention is by no means limited by the following compounds. [chemical 4]
Figure 02_image015
Figure 02_image017
[chemical 5]
Figure 02_image019
[chemical 6]
Figure 02_image021
[chemical 7]
Figure 02_image023
[chemical 8]
Figure 02_image025
[chemical 9]
Figure 02_image027
[chemical 10]
Figure 02_image029
[chemical 11]
Figure 02_image031
[chemical 12]
Figure 02_image033
[chemical 13]
Figure 02_image035
[chemical 14]
Figure 02_image037
[chemical 15]
Figure 02_image039
[chemical 16]
Figure 02_image041
[chemical 17]
Figure 02_image043
[chemical 18]
Figure 02_image045
[chemical 19]
Figure 02_image047
[chemical 20]
Figure 02_image049
[chem 21]
Figure 02_image051
[chem 22]
Figure 02_image053
[chem 23]
Figure 02_image055
[chem 24]
Figure 02_image057
[chem 25]
Figure 02_image059
[Chemical 25A]
Figure 02_image061
The oxime ester compound of the present invention represented by the above general formula (Iα) or (Iβ) is not particularly limited, and can be synthesized, for example, by the method shown below. First, the intermediate of the oxime ester compound of the present invention, that is, the N-aryl compound is obtained. One example of the synthesis method of the N-aryl compound is as follows. That is, a halogenated aryl compound is obtained by reacting a known and commercially available aldehyde compound with a known and commercially available fluorinated benzene compound using potassium carbonate, and by reacting a halogenated aryl compound with a known and commercially available N-containing heterocyclic compounds react to obtain N-aryl compounds. [chem 26]
Figure 02_image063
Next, when n in the general formula (II) is 0, the above-mentioned N-aryl compound can be used, and the oxime compound of the present invention can be produced by the following method according to the following reaction formula. That is, the ketone compound 1 is obtained by reacting the above-mentioned N-aryl compound with an acid chloride, and the oxime compound 1 is obtained by reacting the ketone compound 1 with hydroxylamine hydrochloride. Next, the oxime ester compound 1 of the present invention represented by the above general formula (Iα) or (Iβ) is obtained by reacting an acid anhydride or an acid chloride with the oxime compound 1 . Furthermore, the oxime compound 1 and the oxime ester compound 1 can also be produced by the method described in Japanese Patent No. 4223071. [chem 27]
Figure 02_image065
Also, when n in the general formula (II) is 1, the above-mentioned N-aryl compound can be used, and the oxime compound of the present invention can be produced by the following method according to the following reaction formula. That is, the ketone compound 2 is obtained by reacting the above-mentioned N-aryl compound with an acid chloride, and the oxime compound 2 is obtained by reacting isobutyl nitrite with the ketone compound 2 . Next, the oxime ester compound 2 of the present invention represented by the above general formula (Iα) or (Iβ) is obtained by reacting the acid anhydride or acid chloride with the oxime compound 2 . [chem 28]
Figure 02_image067
Furthermore, in these reaction formulas, the ketone body of the N-containing heterocyclic compound is produced by reacting the amide chloride with the above-mentioned N-containing heterocyclic compound in advance, and the ketone body is used to replace the above-mentioned N-containing heterocyclic compound and the above-mentioned halogenated aryl group. The compounds are reacted, whereby the ketone compound 1 or 2 can also be obtained. The novel oxime ester compound of the present invention described above is useful as a radical polymerization initiator, especially a photopolymerization initiator or a thermal polymerization initiator. Moreover, the novel oxime ester compound of the present invention can also be preferably used as a sensitizer. The photopolymerization initiator of the present invention contains at least one oxime ester compound of the present invention, and may further contain other photopolymerization initiators. The content of the oxime ester compound of this invention in a photopolymerization initiator becomes like this. Preferably it is 30-100 mass %, More preferably, it is 50-100 mass %. The photopolymerization initiator of the present invention is useful as a photopolymerization initiator of an ethylenically unsaturated compound. As other photopolymerization initiators that can be used in combination, previously known compounds can be used, for example: benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzoin , benzoyl dimethyl ketal, 1-benzyl-1-dimethylamino-1-(4'-morpholinylbenzoyl)propane, 2-morpholinyl-2-(4'- Methylmercapto) benzoyl propane, 9-oxosulfur
Figure 107108827-A0304-12-0019-1
Figure 107108827-A0304-xxxx-3
, 1-Chloro-4-propoxy 9-oxosulfur
Figure 107108827-A0304-12-0019-1
Figure 107108827-A0304-xxxx-3
, Isopropyl 9-oxosulfur
Figure 107108827-A0304-12-0019-1
Figure 107108827-A0304-xxxx-3
, Diethyl 9-oxosulfur
Figure 107108827-A0304-12-0019-1
Figure 107108827-A0304-xxxx-3
, Ethyl anthraquinone, 4-benzoyl-4'-methyl diphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2-(4'- Isopropyl)benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis(9 '-acridyl)heptane, 9-n-butyl-3,6-bis(2'-morpholinoisobutyryl)carbazole, 2-methyl-4,6-bis(trichloromethyl)- S-Trisone, 2-Phenyl-4,6-bis(trichloromethyl)-S-Trisone, 2-Naphthyl-4,6-bis(trichloromethyl)-S-Trisone, 2,2- Bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1-2'-biimidazole, 4,4-azobisisobutyronitrile, triphenylphosphine, camphorquinone, N-1414, N-1717, N-1919, NCI-831, NCI-930 (manufactured by ADEKA), IRGACURE369, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02 (manufactured by BASF), benzoyl peroxide, butyl Compounds represented by the general formula (IV) and the like. In addition, these photoinitiators can be used 1 type or in combination of 2 or more types. [chem 29]
Figure 02_image069
(wherein, R 61 and R 62 independently represent cyano group, alkyl group with 1 to 20 carbon atoms, aryl group with 6 to 30 carbon atoms, aralkyl group with 7 to 30 carbon atoms or 2 to 20 heterocyclic groups; R 63 and R 64 independently represent a halogen atom, nitro, cyano, hydroxyl, carboxyl, R 65 , OR 66 , SR 67 , NR 68 R 69 , COR 70 , SOR 71 , SO 2 R 72 or CONR 73 R 74 ; R 63 and R 64 are sometimes bonded to each other to form a ring; R 63 and R 64 may be the same or sometimes different when there are multiple of them; R 65 , R 66 , R 67 , R 68 , R 69 , R 70 , R 71 , R 72 , R 73 and R 74 each independently represent an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, a carbon An aralkyl group with 7 to 30 atoms or a heterocyclic group with 2 to 20 carbon atoms; X 4 represents a direct bond or CO; X 5 represents an oxygen atom, sulfur atom, selenium atom, CR 75 R 76 , CO, or PR 77 ; R 75 , R 76 and R 77 independently represent an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms or an aralkyl group with 7 to 30 carbon atoms; the alkyl or aryl The hydrogen atom in the alkyl group is sometimes replaced by a halogen atom, nitro, cyano group, hydroxyl group, carboxyl group or heterocyclic group; the methylene group in the alkyl or aralkyl group is sometimes replaced by -O-; a represents an integer of 0 to 4; b represents an integer of 0 to 5). Next, the photosensitive composition of this invention is demonstrated. The photosensitive composition of the present invention contains the photopolymerization initiator (A) and the ethylenically unsaturated compound (B) of the present invention and contains a colorant (C), an alkali-developing compound (D), a solvent, or Any additives mentioned below are optional components. In the photosensitive composition of the present invention, the content of the photopolymerization initiator (A) is not particularly limited, but it is preferably 1 to 70 parts by mass, more preferably 100 parts by mass of the ethylenically unsaturated compound (B). 1 to 50 parts by mass, preferably 5 to 30 parts by mass. The above-mentioned ethylenically unsaturated compound (B) will not be particularly limited as long as it has an ethylenically unsaturated bond, and those previously used in photosensitive compositions can be used. Examples include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; (meth)acrylic acid, α-chloroacrylic acid, itaconic acid , maleic acid, citraconic acid, fumaric acid, bicycloheptenedicarboxylic acid, crotonic acid, methacrylic acid, ethylene acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid Mono[2-(meth)acryloxyethyl]ester, Mono[2-(meth)acryloxyethyl]phthalate, ω-carboxypolycaprolactone mono(methyl) Mono(meth)acrylate of a polymer having carboxyl and hydroxyl groups at both ends, such as acrylate; hydroxyethyl (meth)acrylate・maleic acid ester, hydroxypropyl (meth)acrylate・maleic acid ester Unsaturated polyacids such as acid esters, dicyclopentadiene maleate or polyfunctional (meth)acrylates with one carboxyl group and two or more (meth)acryl groups; (methyl) 2-Hydroxyethyl acrylate, 2-Hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, the following compounds No.A1~No.A4, methyl (meth)acrylate, (meth)acrylate base) butyl acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isobutyl (meth)acrylate Octyl ester, isononyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, methoxyethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate Ester, dimethylaminoethyl (meth)acrylate, aminopropyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ethoxyethyl (meth)acrylate, (meth) ) poly(ethoxy)ethyl acrylate, butoxyethoxyethyl (meth)acrylate, ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate, (meth) Tetrahydrofuryl acrylate, Vinyl (meth)acrylate, Allyl (meth)acrylate, Benzyl (meth)acrylate, Ethylene glycol di(meth)acrylate, Diethylene glycol di(meth)acrylate ester, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipenteoerythritol hexa(meth)acrylate base) acrylate, dipentyl penta(meth)acrylate, neopentylthritol tetra(meth)acrylate, neopentylthritol tri(meth)acrylate, tricyclodecane dimethanol di( Esters of unsaturated monobasic acids and polyols or polyphenols such as meth)acrylates, tris[(meth)acrylethyl]isocyanurate, polyester (meth)acrylate oligomers; base) metal salts of unsaturated polyacids such as zinc acrylate and magnesium (meth)acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride Anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxytetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrofuryl Anhydrides of unsaturated polybasic acids such as hydrogen phthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methylbicycloheptenedicarboxylic anhydride; (meth)acrylamide, methylene Bis-(meth)acrylamide, diethylenetriaminetri(meth)acrylamide, xylylenedimethylbis(meth)acrylamide, α-chloroacrylamide, N-2-hydroxy Amides of unsaturated monobasic acids and polybasic acids such as ethyl (meth)acrylamide; unsaturated aldehydes such as acrolein; (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, allyl cyanide Unsaturated nitriles such as radicals; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyl Unsaturated aromatic compounds such as toluene, vinyl benzoic acid, vinyl phenol, vinyl sulfonic acid, 4-vinylbenzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; methyl vinyl Unsaturated ketones such as ketones; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone, vinylpiperidine, etc.; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl methyl ether, vinyl Ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether and other vinyl ethers; maleimide, N-phenylmaleimide, N-cyclohexyl butylene Unsaturated imines such as alkene imides; indenes such as indene and 1-methylindene; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, polysiloxane and other macromonomers with mono(meth)acryloyl groups at the end of polymer molecular chains; Vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl sulfide, vinyl imidazole, vinyl oxazole Phyloline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl urethane compounds of hydroxyl-containing vinyl monomers and polyisocyanate compounds, hydroxyl-containing vinyl monomers, and polyepoxides Compound vinyl epoxy compound. [chem 30]
Figure 02_image071
[chem 31]
Figure 02_image073
[chem 32]
Figure 02_image075
[chem 33]
Figure 02_image077
As the above-mentioned ethylenically unsaturated compound (B), commercially available items can also be used, and examples of commercially available items include: Kayarad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (Nippon Chemical Co., Ltd. Pharmaceutical manufacturing), SPC-1000, SPC-3000 (manufactured by Showa Denko), ARONIX M-140, M-215, M-350 (manufactured by Toagosei), NK Ester A-DPHA-TMPT, A-DCP, A- HD-N, A-9300, TMPT, DCP, NPG, and HD-N (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), etc. Preferred are mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends of these ethylenically unsaturated compounds, and polyfunctional (meth)acryl groups having one carboxyl group and two or more (meth)acryl groups. The photopolymerization initiator of the oxime ester compound of this invention is contained in the ester of meth)acrylate, an unsaturated monobasic acid, and a polyhydric alcohol or a polyphenol. The ethylenically unsaturated compound may be used alone or in combination of two or more, and when using in combination of two or more, these may be previously copolymerized and used as a copolymer. The photosensitive composition of this invention can further contain a coloring agent (C), and can be set as a colored photosensitive composition. Pigments, dyes, natural colorants, etc. are mentioned as this coloring agent (C). These coloring agents may be used alone or in combination of two or more. As the above-mentioned pigments, for example, nitroso compounds; nitro compounds; azo compounds; diazo compounds;
Figure 107108827-A0304-12-0019-1
Figure 107108827-A0304-xxxx-3
Compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; phthalocyanine compounds; isoindolinone compounds; isoindoline compounds; quinacridone compounds; anthracenthrone compounds; pyrene compounds; perylene compounds; pyrrole Diketopyrrole compounds; thioindigo compounds; dioxane compounds; triphenylmethane compounds; quinophthalone compounds; naphthalene tetracarboxylic acid; metal complexes of azo dyes and cyanine dyes; lake pigments; by furnace method , carbon black obtained by channel method or thermal method, or carbon black such as acetylene black, ketjen black or lamp black; those prepared by epoxy resin or coated with the above carbon black, the above carbon black is pre-prepared Dissolved in a solvent and dispersed in a resin to absorb 20 to 200 mg/g of the resin, the above-mentioned carbon black has been subjected to acidic or alkaline surface treatment, the average particle size is 8 nm or more and DBP (Dibutyl phthalate, dibutyl phthalate) carbon black with an oil absorption of 90 ml/100 g or less, the total oxygen content calculated from the CO and CO 2 in the volatile matter at 950°C is per 100 m 2 surface area Carbon black above 9 mg; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, spiral carbon fiber, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black ;Chrome oxide green, Milori blue, cobalt green, cobalt blue, manganese series, ferrocyanide, phosphate ultramarine blue, iron blue, ultramarine blue, sky blue, dark green, emerald green, lead sulfate, yellow lead, zinc yellow, Iron red (iron oxide red (III)), cadmium red, synthetic iron black, umber and other organic or inorganic pigments. These pigments can be used individually or in mixture of several types. As the above-mentioned pigment, commercially available pigments can 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. Examples of the aforementioned dyes include: azo dyes, anthraquinone dyes, indigo dyes, triarylmethane dyes,
Figure 107108827-A0304-12-0019-1
Figure 107108827-A0304-xxxx-3
Dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, 㗁𠯤 dyes, phthalocyanine dyes, cyanine dyes, etc. Sometimes they are used alone, and sometimes they are used in combination. In the photosensitive composition of this invention, content of the said coloring agent (C) is preferably 5-100 mass parts with respect to 100 mass parts of said ethylenically unsaturated compounds (B), More preferably, it is 10-50 mass parts. The photosensitive composition of this invention can further contain an alkali-developable compound (D), and can be set as an alkali-developable photosensitive resin composition. What contains both a coloring agent (C) and an alkali-developable compound (D) is also called a colored alkali-developable photosensitive resin composition. As said alkali-developable compound (D), it will not specifically limit if it is a compound soluble in alkaline aqueous solution, For example, the resin etc. which were described in Unexamined-Japanese-Patent No. 2004-264414 are mentioned. Also, as the above-mentioned alkali-developable compound (D), copolymers of acrylates, or phenol and/or cresol novolak epoxy resins, polyphenylmethane-type epoxy resins having polyfunctional epoxy groups, cyclo Oxyacrylate resin, a resin obtained by reacting an unsaturated monobasic acid with an epoxy group of an epoxy compound such as an epoxy compound represented by the following general formula (V), and further allowing a polybasic acid anhydride to react with it. The so-called epoxy acrylate resin described here is obtained by allowing (meth)acrylic acid to react with the above-mentioned epoxy compound. Examples thereof include Ripoxy SPC-2000, DICLITE UE-777 manufactured by DIC Corporation, Japan U-PICA company manufactures U-PICA 4015 and so on. Among them, it is preferable to make unsaturated monobasic acid react with epoxy acrylate resin and the epoxy group of the epoxy compound represented by the following general formula (V), and then make polybasic acid anhydride react with it. obtained resin. [chem 34]
Figure 02_image079
(wherein, X6 represents a direct bond, methylene group, alkylene group with 1 to 4 carbon atoms, alicyclic hydrocarbon group with 3 to 20 carbon atoms, -O-, -S-, -SO- 2 , -SS-, -SO-, -CO-, -OCO- or the group represented by the following [Chemical 35-1], [Chemical 35-2] or [Chemical 35-3], and the above-mentioned alkylene group sometimes is substituted by a halogen atom, R 81 and R 82 independently represent an alkyl group with 1 to 5 carbon atoms, an alkoxy group with 1 to 8 carbon atoms, an alkenyl group with 2 to 5 carbon atoms or a halogen atom, and The above-mentioned alkyl, alkoxy and alkenyl groups are sometimes substituted with halogen atoms; R 81 and R 82 may be the same or different when there are plural numbers of each; c is an integer of 0 to 4; d is an integer of 0 to 4; m is an integer of 0 to 10; when m is not 0, there are optical isomers, any isomers are acceptable). [Chemical 35-1]
Figure 02_image081
(In the formula, Z3 represents a hydrogen atom, a phenyl group sometimes substituted by an alkyl group with 1 to 10 carbon atoms or an alkoxy group with 1 to 10 carbon atoms, or a phenyl group sometimes substituted with an alkyl group with 1 to 10 carbon atoms Alkyl group having 10 or alkoxy group having 1~10 carbon atoms, cycloalkyl group having 3~10 carbon atoms, Y1 represents alkyl group having 1~10 carbon atoms, alkoxy group having 1~10 carbon atoms , an alkenyl group having 2 to 10 carbon atoms or a halogen atom, the above-mentioned alkyl, alkoxy and alkenyl groups may be substituted with a halogen atom, and d is an integer of 0 to 5). [Chemical 35-2]
Figure 02_image083
[chem 35-3]
Figure 02_image085
(wherein, Y2 and Z4 each independently represent an alkyl group with 1 to 10 carbon atoms sometimes substituted by a halogen atom, an aryl group with 6 to 20 carbon atoms sometimes substituted by a halogen atom, An aryloxy group with 6 to 20 carbon atoms sometimes substituted by a halogen atom, an arylthio group with 6 to 20 carbon atoms sometimes substituted by a halogen atom, and an arylthio group with 6 to 20 carbon atoms sometimes substituted by a halogen atom 20 arylalkenyl group, aralkyl group with 7 to 20 carbon atoms sometimes substituted by halogen atom, heterocyclic group with 2 to 20 carbon atoms sometimes substituted with halogen atom, or halogen atom, and The alkylene part in the above-mentioned alkyl group and aralkyl group is sometimes interrupted by an unsaturated bond, -O- or -S-, Z 4 sometimes forms a ring with adjacent Z 4 , p represents an integer of 0 to 4, q represents an integer of 0 to 8, r represents an integer of 0 to 4, s represents an integer of 0 to 4, and the sum of the numbers of r and s is an integer of 2 to 4). Examples of the above-mentioned unsaturated monobasic acid that reacts with the epoxy compound include: acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate maleate, Hydroxyethyl Acrylate・Maleate, Hydroxypropyl Methacrylate・Maleate, Hydroxypropyl Acrylate・Maleate, Dicyclopentadiene・Maleate wait. As the above-mentioned polybasic acid anhydride that is allowed to act after the above-mentioned unsaturated monobasic acid is acted on, biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphenyltetracarboxylic dianhydride, maleic acid anhydride, Alkenic Anhydride, Trimellitic Anhydride, Pyromellitic Anhydride, 2,2'-3,3'-Benzophenone Tetracarboxylic Anhydride, Ethylene Glycol Dihydrotrimellitate, Glycerol Trimellitic Trimellitic Anhydride esters, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, acetic anhydride, methyl phthalic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5-(2,5-dioxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride Products, dodecenyl succinic anhydride, methyl bicycloheptene dicarboxylic anhydride, etc. The reaction molar ratio of the said epoxy compound, the said unsaturated monobasic acid, and the said polybasic acid anhydride is preferably set as follows. That is, in an epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of the above-mentioned unsaturated monobasic acid are added to one epoxy group of the above-mentioned epoxy compound, it is preferable to make the ratio as follows: One hydroxyl group of this epoxy adduct has 0.1 to 1.0 pieces of the acid anhydride structure of the said polybasic acid anhydride. The reaction of the above-mentioned epoxy compound, the above-mentioned unsaturated monobasic acid, and the above-mentioned polybasic acid anhydride can be carried out according to a conventional method. Moreover, an alkali-developable compound may have an ethylenically unsaturated bond. That is, the above-mentioned ethylenically unsaturated compound (B) and the above-mentioned alkali-developable compound (D) may be the same compound. In this case, it is preferable that the compound which has alkali developability and has an ethylenically unsaturated bond contains 0.2-1.0 equivalent of unsaturated groups. Furthermore, when using the compound which has alkali developability and has an ethylenically unsaturated bond, when calculating the content of the said photoinitiator (A) and content of the coloring agent (C) about this compound, Let it be contained in an ethylenically unsaturated compound (B). When the photosensitive composition of the present invention is made into an alkali-developable photosensitive resin composition, the content of the above-mentioned alkali-developable compound (D) which may have an ethylenically unsaturated bond is defined in the present invention. In the alkali-developable photosensitive resin composition, it is preferable that it is 1-20 mass %, especially 3-12 mass %. In order to adjust the acid value and improve the developability of the (colored) alkali-developable photosensitive resin composition of the present invention, it can be used together with the above-mentioned alkali-developable compound (D) which may have an ethylenically unsaturated bond Monofunctional or polyfunctional epoxy compounds. The alkali-developable compound (D) sometimes having an ethylenically unsaturated bond is preferably in the range of 5 to 120 mgKOH/g in the acid value of the solid content, and the usage amount of the monofunctional or polyfunctional epoxy compound is preferable It is selected so as to satisfy the above-mentioned acid value. 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, Butyl glycidyl ether, tertiary 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, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethyl Hexyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxyglycidyl ether, p-butylphenol glycidyl ether Ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether Glyceryl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monoxide, 1,2-epoxy-4-ethylene Cyclohexane, styrene oxide, pinene oxide, methyl styrene oxide, cyclohexane oxide, propylene oxide, the above compounds No.A2, No.A3, etc. If one or more compounds selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers are used as the above-mentioned polyfunctional epoxy compound, an alkali-developable photosensitive compound (colored) with better characteristics can be obtained. Resin composition, thus preferred. As said bisphenol type epoxy compound, other than the epoxy compound represented by the said general formula (V), bisphenol type epoxy compounds, such as hydrogenated bisphenol type epoxy compound, can also be used, for example. In addition, as the glycidyl ethers mentioned above, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether , triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri( Glycidyloxymethyl) propane, 1,1,1-tris(glycidyloxymethyl)ethane, 1,1,1-tris(glycidyloxymethyl)methane, 1,1,1, 1-Tetrakis(glycidyloxymethyl)methane and the like. In addition, phenol novolak type epoxy compounds, biphenyl novolac type epoxy compounds, cresol novolac type epoxy compounds, bisphenol A novolac type epoxy compounds, dicyclopentadiene novolak type epoxy compounds, Novolak-type epoxy compounds such as epoxy compounds; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-cyclohexane Alicyclic epoxy compounds such as oxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 1-oxiranyl-3,4-epoxycyclohexane; diglycidyl phthalate glycidyl esters, diglycidyl tetrahydrophthalate, glycidyl dimer acid and other glycidyl esters; tetraglycidyl diaminodiphenylmethane, triglycidyl p-aminophenol, N,N-di Glycidyl amines such as glycidyl aniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethyl allantoin and triglycidyl isocyanurate; Dioxide compounds such as pentadiene; naphthalene-type epoxy compounds; triphenylmethane-type epoxy compounds; dicyclopentadiene-type epoxy compounds, etc. The photosensitive composition of this invention can further contain a solvent. As the solvent, solvents that can dissolve or disperse the above-mentioned components (photopolymerization initiator (A) and ethylenically unsaturated compound (B), etc.) if necessary, such as methyl ethyl ketone, methyl pentyl Diethyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and other ketones; ether, dioxane, tetrahydrofuran, 1,2-dimethyl Ether solvents such as oxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, Ester solvents such as cyclohexyl acetate, ethyl lactate, dimethyl succinate, and TEXANOL; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol, ethanol, iso- or n-propanol, Alcohol solvents such as iso-or n-butanol and pentanol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), di Propylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, ethoxy ethyl ether propionate and other ether ester solvents; Benzene, toluene, xylene and other BTX (Benzene-Toluene-Xylene, benzene, toluene , xylene) solvents; aliphatic hydrocarbon solvents such as hexane, heptane, octane, cyclohexane, etc.; terpene hydrocarbon oils such as turpentine, D-limonene, pinene, etc.; mineral spirits, Swazol#310 (Cosmo Matsuyama Oil Company), Solvesso#100 (Exxon Chemical Company) and other alkane-based solvents; carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane and other halogenated aliphatic hydrocarbon-based solvents; chlorine Halogenated aromatic hydrocarbon solvents such as benzene; carbitol-based solvents; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N,N-dimethylformamide; N,N-dimethylacetamide Amine (DMAc); N-methylpyrrolidone; dimethylsulfoxide; water, etc.; these solvents may be used alone or as a mixed solvent of two or more. Among these, ketones, ether-ester solvents, etc., especially propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, etc., are preferred because in the photosensitive composition, they are resistant to The compatibility between the etchant and the photopolymerization initiator (A) is better. In the photosensitive composition of this invention, although content of a solvent is not specifically limited, Preferably it is 30-95 mass % in 100 mass % of photosensitive composition whole quantities, More preferably, it is 50-95 mass %. When the content of the solvent is within the above-mentioned range, it becomes operability (viscosity or wettability of the photosensitive composition), reduction of unevenness during drying, and liquid stability (without precipitation of components contained in the composition). or precipitation) excellent photosensitive composition can properly control the thickness of the cured product when obtaining the cured product, so it is preferable. In addition, p-anisole, hydroquinone, catechol, tertiary butylcatechol, inorganic compounds, latent additives, organic polymers, chain transfer agents may be added to the photosensitive composition of the present invention as needed , sensitizer, surfactant, silane coupling agent, melamine compound, thermal polymerization inhibitor; plasticizer; adhesion accelerator; filler; defoamer; leveling agent; surface regulator; antioxidant; ultraviolet absorber ; Dispersant, dispersant aid; Dispersing ink agent; Anti-agglomeration agent; Catalyst; Hardening accelerator; Cross-linking agent; A dispersant for dispersing a colorant (C) and/or an inorganic compound may be added to the photosensitive composition of the present invention. The dispersant is not limited as long as it can disperse and stabilize the colorant (C) or the inorganic compound, and commercially available dispersants such as BYK series manufactured by BYK-Chemie can be used. In particular, polymer dispersants comprising polyesters, polyethers, or polyurethanes with basic functional groups can be preferably used, especially if the basic functional groups are amines and/or their quaternary salts and The amine value is 1-100 mgKOH/g. The so-called latent additive mentioned above means that it is inert in the light exposure step and the pre-baking step at room temperature and is heated at 100-250°C, or carried out at 80-200°C in the presence of an acid/alkaline catalyst. When heated, the protective group will be detached and activated. Examples of effects obtained by activation include anti-oxidation, ultraviolet absorption, antifouling properties, recoatability, and adhesiveness. As the above-mentioned latent additives, those described in the specification of International Publication No. 2014/021023 can be preferably used. As a preferable example of the above-mentioned latent additives, in addition to the latent additives described in the specification of International Publication No. 2014/021023, those represented by the following general formulas (A) to (C) can also be mentioned. [chem 36]
Figure 02_image087
(In the formula, ring A1 is an alicyclic ring, aromatic ring or heterocyclic ring of a six-membered ring; R 81 , R 82 , R 83 , R 84 and R 85 represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, Carboxyl group, alkyl group with 1 to 40 carbon atoms which may have substituents, aryl group with 6 to 20 carbon atoms, aralkyl group with 7 to 20 carbon atoms or heterocyclic ring-containing group with 2 to 20 carbon atoms group, or -OR 86 , at least one of R 81 , R 82 , R 83 , R 84 and R 85 is not a hydrogen atom; R 86 represents an alkyl group with 1 to 20 carbon atoms, and an alkyl group with 2 to 20 carbon atoms alkenyl group, aryl group with 6 to 20 carbon atoms, aralkyl group with 7 to 20 carbon atoms, heterocyclic group with 2 to 20 carbon atoms or trialkylsilyl group). [chem 37]
Figure 02_image089
(In the formula, ring A 1 is the same as the above-mentioned general formula (A), R 91 is the same as R 86 of the above-mentioned general formula (A); X 7 is a group represented by the following general formula (1); R 92 , R 93 , R 94 and R 95 represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group with 1 to 40 carbon atoms sometimes having a substituent, an aryl group with 6 to 20 carbon atoms, a carbon An aralkyl group having 7 to 20 atoms or a heterocyclic ring-containing group having 2 to 20 carbon atoms, at least one of R 92 , R 93 , R 94 and R 95 is not a hydrogen atom). [chem 38]
Figure 02_image091
(In the above general formula (1), X 8 represents -CR 97 R 98 -, -NR 99 -, a divalent aliphatic hydrocarbon group with 1 to 35 carbon atoms, an aromatic hydrocarbon group with 6 to 35 carbon atoms, or carbon A heterocyclic group with 2 to 35 atoms, or any group shown in the following [Chemical 39] [Chemical 40-1] [Chemical 40-2]; the methylene group in the aliphatic hydrocarbon group is sometimes substituted by -O-, -S-, -CO-, -COO-, -OCO- or -NH-, or in the case of non-adjacent oxygen atoms are substituted with a bonding group formed by combining them; R 97 and R98 represents a hydrogen atom, an alkyl group with 1 to 8 carbon atoms, an aryl group with 6 to 20 carbon atoms, or an aralkyl group with 7 to 20 carbon atoms; Z5 and Z6 independently represent a direct bond, -O-, -S-, -CO-, -CO-O-, -O-CO-, -SO 2 -, -SS-, -SO- or -NR 100 -; R 99 and R 100 represent hydrogen atoms , an aliphatic hydrocarbon group with 1 to 35 carbon atoms sometimes having a substituent, an aromatic hydrocarbon group with 6 to 35 carbon atoms sometimes having a substituent, or a heterocyclic ring with 2 to 35 carbon atoms sometimes having a substituent base; * indicates a bonding bond). [chem 39]
Figure 02_image093
(In the above formula, R 101 represents a hydrogen atom, a phenyl group sometimes having a substituent, or a cycloalkyl group with 3 to 10 carbon atoms, R 102 represents an alkyl group with 1 to 10 carbon atoms, and an alkyl group with 1 to 10 carbon atoms alkoxy, alkenyl having 2 to 10 carbon atoms or a halogen atom, the above-mentioned alkyl, alkoxy and alkenyl may have substituents, f is an integer of 0 to 5, and * represents a bond). [Chem. 40-1]
Figure 02_image095
(In the formula, * represents a bonding bond). [chemical 40-2]
Figure 02_image097
(In the above formula, R 103 and R 104 each independently represent an alkyl group with 1 to 10 carbon atoms that may have a substituent, an aryl group with 6 to 20 carbon atoms that may have a substituent, or an aryl group that may have a substituent Aryloxy group having 6 to 20 carbon atoms as a group, arylthio group having 6 to 20 carbon atoms sometimes having a substituent, arylalkenyl group having 6 to 20 carbon atoms sometimes having a substituent, sometimes An aralkyl group with 7 to 20 carbon atoms having a substituent, a heterocyclic group with 2 to 20 carbon atoms or a halogen atom having a substituent, and the methylene group in the alkyl group and aralkyl group may be Unsaturated bond, -O- or -S-interruption, R 103 sometimes forms a ring with adjacent R 103 , b represents the number from 0 to 4, c represents the number from 0 to 8, g represents the number from 0 to 4, h represents a number from 0 to 4, and the sum of the numbers from g and h is 2 to 4). [chem 41]
Figure 02_image099
(wherein, k=2～6, X 9 is the base represented by the above-mentioned general formula (1) when k=2, the base represented by the following general formula (2) when k=3, the following when k=4 The base represented by the general formula (3), the following general formula (4) when k=5, and the following general formula (5) when k=6; R 111 , R 112 , R 113 and R 114 represent hydrogen atom, halogen atom, cyano group, hydroxyl group, nitro group, carboxyl group, or an alkyl group with 1 to 40 carbon atoms, an aryl group with 6 to 20 carbon atoms, an aralkyl group with 7 to 20 carbon atoms or In a heterocyclic ring-containing group having 2 to 20 carbon atoms, at least one of R 111 , R 112 , R 113 and R 114 is not a hydrogen atom; ring A 1 and R 86 are the same as the above general formula (A)). [chem 42]
Figure 02_image101
(In the above general formula (2), Y11 represents a trivalent aliphatic hydrocarbon group with 1 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 group with 2 to 35 atoms; Z 11 , Z 12 and Z 13 each independently represent a direct bond, -O-, -S-, -CO-, -CO-O-, -O-CO-, - SO 2 -, -SS-, -SO-, -NR 121 -, -PR 121 -, an aliphatic hydrocarbon group with 1 to 35 carbon atoms that may have a substituent, and a carbon atom group with 6 to 35 carbon atoms that may have a substituent 35 aromatic hydrocarbon group, or a heterocyclic group with 2 to 35 carbon atoms sometimes having a substituent; R 121 represents a hydrogen atom, an aliphatic hydrocarbon group with 1 to 35 carbon atoms sometimes having a substituent, An aromatic hydrocarbon group with 6 to 35 carbon atoms in the substituent or a heterocyclic group with 2 to 35 carbon atoms in the substituent, and the methylene group in the aliphatic hydrocarbon group is sometimes substituted with a carbon-carbon double bond , -O-, -CO-, -O-CO-, -CO-O- or -SO 2 -). [chem 43]
Figure 02_image103
(In the above general formula (3), Y12 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 a heterocyclic ring with 2 to 35 carbon atoms group; the methylene group in the aliphatic hydrocarbon group is sometimes substituted by -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-; Z 11 ~ Z 14 are independently The same range as the groups represented by Z 11 to Z 13 in the general formula (2) above). [chem 44]
Figure 02_image105
(In the above general formula (4), Y represents a pentavalent aliphatic hydrocarbon group with 2 to 35 carbon atoms, an aromatic hydrocarbon group with 6 to 30 carbon atoms, or a heterocyclic group with 2 to 30 carbon atoms; the aliphatic The hydrocarbon group is sometimes interrupted by -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-; Z 11 ~ Z 15 are independently the same as Z 11 ~ Z of the above general formula (2). A group within the same range as the group represented by Z13 ). [chem 45]
Figure 02_image107
(In the above general formula (5), Y represents a hexavalent aliphatic hydrocarbon group with 2 to 35 carbon atoms, an aromatic hydrocarbon group with 6 to 35 carbon atoms or a heterocyclic group with 2 to 35 carbon atoms; the aliphatic The hydrocarbon group is sometimes interrupted by -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-; Z 11 to Z 16 are independently the same as Z 11 to Z of the above general formula (2). A group within the same range as the group represented by Z13 ). Moreover, the characteristic of hardened|cured material can also be improved by using the said organic polymer (other than an ethylenically unsaturated compound (B) and an alkali-developable compound (D)). Examples of such organic polymers 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 (acrylonitrile-butadiene-styrene, propylene-butadiene-styrene ) resin, nylon 6, nylon 66, nylon 12, urethane 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 preferable. When using an organic polymer, it is preferable that the usage-amount is 10-500 mass parts with respect to 100 mass parts of ethylenically unsaturated compounds (B). As the above-mentioned chain transfer agent or the above-mentioned sensitizer, a sulfur atom-containing compound is generally used. Examples include 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)aminoformyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-( 3-mercaptopropionyl)alanine acid, 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, 2-mercapto-3-pyridyl alcohol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), etc. Disulfide compounds obtained by oxidation of mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid and other iodide alkyl compounds, trimethylolpropane tri( 3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol dithiopropane Ester, Butylene Glycol Dithioglycolate, Ethylene Glycol Dithioglycolate, Trimethylolpropane Trithioglycolate, Butylene Glycol Dithiopropionate, Trimethylolpropane Trithiopropionate, Trimethylolpropane Trithioglycolate, Pentaerythritol Tetrathiopropionate, Pentaerythritol Tetrathioglycolate, Trihydroxyethyl Trithiopropionate, Diethyl 9 -Oxysulfur
Figure 107108827-A0304-12-0019-1
Figure 107108827-A0304-xxxx-3
, Diisopropyl 9-oxosulfur
Figure 107108827-A0304-12-0019-1
Figure 107108827-A0304-xxxx-3
, the following compound No. C1, aliphatic polyfunctional thiol compounds such as trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, Karenz MT BD1, PE1, NR1 manufactured by Showa Denko Co., Ltd., etc. [chem 46]
Figure 02_image109
As the above-mentioned surfactants, fluorine-based surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates; anion-based surfactants such as higher fatty acid alkali metal salts, alkylsulfonates, and alkylsulfates Surfactants; cationic surfactants such as advanced amine halide salts and quaternary ammonium salts; polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides, etc. Nonionic surfactants; amphoteric surfactants; polysiloxane-based surfactants and other surfactants can be used alone or 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 which KBE-9007, KBM-502, KBE-403 and the like can be preferably used. Based silane coupling agent. Examples of the above-mentioned melamine compound include active hydroxyl groups in nitrogen compounds such as (poly)methylol melamine, (poly)methylol glycoluril, (poly)methylol benzoguanamine, and (poly)methylol urea. Compounds in which all or part (at least 2) of methyl groups (CH 2 OH groups) are etherified with alkyl groups, etc. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, or a butyl group, and may be the same as or different from each other. In addition, the methylol group that has not been alkylated may self-condense in one molecule, and may condense between two molecules to form an oligomer component. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril, etc. can be used. Among them, alkyl-etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferred. As said leveling agent, it will not specifically limit if it has a leveling effect, Existing leveling agents can be used, Among them, a silicone type leveling agent and a fluorine type leveling agent can be used especially preferably. As the silicone-based leveling agent, commercially available silicone-based leveling agents can be used, such as BYK-300, BYK-306, BYK-307, BYK-310, BYK-315, BYK-313, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-344, BYK-347, BYK-348, BYK- 349, BYK-370, BYK-375, BYK-377, BYK-378, BYK-UV3500, BYK-UV3510, BYK-UV3570, BYK-3550, BYK-SILCLEAN3700, BYK-SILCLEAN3720 (Above, manufactured by BYK-Chemie Japan) ; ACFS 180, AC FS 360, AC S20 (above, manufactured by Algin Chemie); Polyflow KL-400X, Polyflow KL-400HF, Polyflow KL-401, Polyflow KL-402, Polyflow KL-403, Polyflow KL-404 (above, Kyoeisha Chemical Manufacture); KP-323, KP-326, KP-341, KP-104, KP-110, KP-112 (above, Shin-Etsu Chemical Manufacture); LP-7001, LP-7002, 8032 ADDITIVE, Commercial items such as 57 ADDITIVE, L-7604, FZ-2110, FZ-2105, 67 ADDITIVE, 8618 ADDITIVE, 3 ADDITIVE, 56 ADDITIVE (above, manufactured by Dow Corning Toray). As the above-mentioned fluorine-based leveling agent, commercially available fluorine-based leveling agents can be used, for example, OPTOOL DSX, OPTOOL DAC-HP (manufactured by DAIKIN INDUSTRIES above); Surflon S-242, Surflon S-243, Surflon S-420 , Surflon S-611, Surflon S-651, Surflon S-386 (above, manufactured by AGC Seimi Chemical); BYK-340 (manufactured by BYK-Chemie Japan); AC110a, AC 100a (above, manufactured by Algin Chemie); MEGAFAC F- 114, MEGAFAC F-410, MEGAFAC F-444, MEGAFAC EXPTP-2066, MEGAFAC F-430, MEGAFAC F-472SF, MEGAFAC F-477, MEGAFAC F-552, MEGAFAC F-553, MEGAFAC F-554, MEGAFAC F- 555, MEGAFAC R-94, MEGAFAC RS-72-K, MEGAFAC RS-75, MEGAFAC F-556, MEGAFAC EXPTF-1367, MEGAFAC EXP TF-1437, MEGAFAC F-558, MEGAFAC EXPTF-1537 (Above, manufactured by DIC) ; FC-4430, FC-4432 (above, manufactured by Sumitomo 3M); FTERGENT 100, FTERGENT 100C, FTERGENT 110, FTERGENT 150, FTERGENT 150CH, FTERGENT AK, FTERGENT 501, FTERGENT 250, FTERGENT 251, FTERGENT 222F, FTERG ENT 208G, FTERGENT 300, FTERGENT 310, FTERGENT 400SW (above, manufactured by NEOS); PF-136A, PF-156A, PF-151N, PF-636, PF-6320, PF-656, PF-6520", PF-651, PF-652 , PF-3320 (above, manufactured by Kitamura Chemical Co., Ltd.), etc., are commercially available. In the photosensitive composition of the present invention, in addition to the photopolymerization initiator (A), ethylenically unsaturated compound (B), colorant (C), alkaline developable compound (D), solvent and organic polymer , The amount of optional additives used can be appropriately selected depending on the purpose of use, and is not particularly limited, but is preferably 50 parts by mass or less in total with respect to 100 parts by mass of the above-mentioned ethylenically unsaturated compound (B). The photosensitive composition of the present invention, the alkali-developable photosensitive resin composition or the cured product can be preferably used in display devices, in detail, can be preferably used in display devices (color TV, PC (Personal Computer, personal computer) monitor, portable information terminal, digital camera, etc.) color filter in the liquid crystal display element of the color display. In addition, it can also be used for photocurable paint or varnish; photocurable adhesive; printed substrate; color filter of CCD (Charge Coupled Device, Charge Coupled Device) image sensor; electrode for plasma display panel materials; powder coatings; printing inks; printing plates; adhesives; dental compositions; gel coats; photoresists for electronics; plating resists; etching resists; dry films; solder resists; used to form various Resists for the structure of display devices; 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 ; fiberglass cable coatings; stencils for screen printing; materials for the manufacture of three-dimensional objects by stereolithography; materials for holographic recording; image recording materials; microelectronic circuits; decolorizing materials; materials for image recording decolorizing materials for image recording materials using microcapsules; photoresist materials for printed wiring boards; photoresist materials for UV (ultraviolet, ultraviolet) and visible light laser direct imaging systems; printed circuit substrates Various uses such as photoresist materials and protective films used in the formation of the dielectric layer in the buildup are not particularly limited. The photosensitive composition or alkali-developable photosensitive resin composition of this invention can also be used for the purpose of forming the spacer for liquid crystal display panels, and the purpose of forming the protrusion for vertical alignment type liquid crystal display elements. In particular, it is useful as a photosensitive composition for simultaneous formation of protrusions and spacers for a vertical alignment type liquid crystal display element. The method of producing a cured product using the photosensitive composition or alkali-developing photosensitive resin composition of the present invention will be described in detail below. The photosensitive composition or alkali-developing photosensitive resin composition of this invention can be cured by irradiating energy rays. The photosensitive composition or alkali-developable photosensitive resin composition of the present invention can be coated with a spin coater, roll coater, bar coater, die coater, or curtain before curing. Well-known methods such as machine, various printing, and dipping 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 is not limited. In addition, as the energy ray used for curing the alkali-developable photosensitive resin composition of the photosensitive composition of the present invention, ultrahigh-pressure mercury lamps, high-pressure mercury lamps, medium-pressure mercury lamps, low-pressure mercury lamps, mercury vapor arc lamps, Xenon arc lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light-emitting diodes, CRT (Cathode-Ray Tube, cathode ray tube) light sources and other light sources have Electromagnetic wave energy lines with a wavelength of 2000 angstroms to 7000 angstroms, or high-energy lines such as electron beams, X-rays, and radiation, preferably ultra-high pressure mercury lamps, mercury vapor arc lamps, and carbon arc lamps that emit light with a wavelength of 300-450 nm , xenon arc lamp and other light sources. Furthermore, in terms of improving not only productivity but also resolution and positional accuracy, it is useful to use laser light as an exposure light source and to use digital information from a computer or the like without using a mask. The laser direct writing method that directly forms an image, as its laser light, can preferably use light with a wavelength of 340-430 nm, and can also use excimer laser, nitrogen laser, argon ion laser, helium-cadmium Lasers, helium-neon lasers, krypton ion lasers, various semiconductor lasers and YAG (Yttrium Aluminum Garnet, yttrium-aluminum-garnet) lasers that emit light in the region of visible light to infrared light. In the case of using such lasers, a sensitizing pigment that absorbs light in the region from visible light to infrared light may be added. In addition, the above-mentioned spacers for liquid crystal display panels can be preferably formed by the following steps: (1) forming a coating film of the photosensitive composition of the present invention on a substrate; The coating film is irradiated with radiation; (3) baking after exposure; (4) developing the coating film after exposure; and (5) heating the coating film after development. Also, the photosensitive composition of the present invention is useful as a partition wall forming resin composition for an inkjet system when it contains an ink repelling agent, and the composition can be used as a color filter, and particularly preferably Partition walls for inkjet color filters with a profile angle of 50° or more. As the ink repelling agent, a composition containing a fluorine-based surfactant and a fluorine-based surfactant can be preferably used. When the photosensitive composition of the present invention is made into a person containing an ink-repelling agent and used as the above-mentioned partition wall forming resin composition for an inkjet method, an optical element can be produced by the following method: Partitions are formed to divide the transferred body, and liquid droplets are applied to the concave portions of the divided transferred body by an inkjet method to form image regions. At this time, it is preferable that the above-mentioned liquid droplets contain a colorant to color the above-mentioned image region, thereby obtaining a substrate having at least a pixel group including a plurality of colored regions and a partition wall separating each colored region of the pixel group. Optical element. EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in more detail, this invention is not limited to these Examples etc. [Example 1] Production of compound No.1 (step 1) Production of intermediate 1A (halogenated aryl compound) Weigh 2-chloro-4'-fluoroacetophenone (3.59 g), salicylic aldehyde ( 5.08 g), potassium carbonate (5.75 g), and acetone (15 g) into a 100 ml four-neck flask, and heated to reflux for 1 hour. After cooling to room temperature, ion-exchanged water (41.6 g) was added, and the precipitate was collected by filtration and sufficiently dried to obtain Intermediate 1A (4.74 g: yield 95%) as a pale yellow solid. [chem 47]
Figure 02_image111
(Step 2) Production of intermediate 1B (ketone compound) Weigh intermediate 1A (4.42 g), the following indole compound 1A (4.07 g), potassium carbonate (4.62 g) and DMAc (23.25 g) to 100 ml After placing in a four-necked flask, the reaction was carried out at 110° C. for 3 hours. Ion-exchanged water (15.5 g) and ethyl acetate (23.25 g) were added, oil and water were separated, and the organic layer was washed with water three times to remove the solvent. Then, ethyl acetate (15.5 g) and hexane (23.25 g) were added to the obtained residue, it heat-dissolved, and it cooled and recrystallized. After cooling to 5° C., the precipitate was collected by filtration and sufficiently dried to obtain Intermediate 1B (6.8 g: yield 87%) as a white solid. [chem 48]
Figure 02_image113
[chem 49]
Figure 02_image115
(Step 3) Production of intermediate 1C (oxime compound) Weigh intermediate 1B (3.74 g) and DMF (12.93 g) into a 30 ml two-necked flask, and add 35% hydrochloric acid 1.26 dropwise while stirring at 5°C. g and isobutyl nitrite 0.87 g, and stirred at room temperature for 30 hours. Ion-exchanged water (11.9 g) and ethyl acetate (11.9 g) were added for oil-water separation, and the organic layer was washed three times with water. After the organic layer was desolvated, it was purified with a silica gel column (ethyl acetate/hexane=1/9) to obtain Intermediate 1C (3.0 g: yield 75%) as a pale yellow solid. [chemical 50]
Figure 02_image117
(Step 4) Preparation of Compound No.1 (the oxime ester compound of the present invention) Weigh the intermediate 1C (2.21 g) and THF (7.2 g) into 30 ml 2-necked round-bottomed flasks, and place them under nitrogen flow and ice Acetyl chloride (2.12 g) and triethylamine (2.72 g) were added dropwise under cooling in a bath, followed by stirring at room temperature for 1 hour. Ion-exchanged water (7.2 g) and ethyl acetate (7.2 g) were added for oil-water separation, and the organic layer was washed three times with water. After the organic layer was desolventized, it was purified with a silica gel column (ethyl acetate/hexane) to obtain Compound No. 1 (1.5 g: yield 63%) as a pale yellow solid. The analysis results of the obtained compound No. 1 are shown in [Table 1] to [Table 3]. In addition, OXE 02 described together in [Table 1] is a commercially available photopolymerization initiator used in Comparative Example 1 described later. [Chemical 51]
Figure 02_image119
[Example 2] Production of Compound No. 189 (Step 1) Production of Intermediate 2A Add 9.6 g of the above intermediate 1B, 30.0 g of dimethylacetamide, and 2.2 g of hydroxylamine hydrochloride, and then add at 60°C Sodium hydroxide 1.2 g. It was made to react at 60 degreeC for 2 hours, after that, ion-exchange water and chloroform were added, and it extracted while heating. The organic layer was washed 3 times with water, and purified by a silica gel column (ethyl acetate/hexane=1/6) after desolventization to obtain the following intermediate 2A (2.0 g: yield 25%). [Chemical 52]
Figure 02_image121
(Step 2) Production of Compound No. 189 (Oxime Ester Compound of the Present Invention) Compound No. 189 was obtained in the same manner as in Step 4 of Example 1 except that Intermediate 1C was changed to Intermediate 2A. [Example 3] Production of Compound No. 190 (Step 1) Production of Intermediate 3B It was obtained in the same manner as in Step 2 of Example 1, except that the indole compound 1A was changed to the following carbazole compound 3A. Intermediate 3B below. [Chemical 53]
Figure 02_image123
(Step 2) Production of Intermediate 3C Add 2.72 g of aluminum chloride and 30.0 g of dichloroethane to a 100 ml four-neck flask, add 7.54 g of Intermediate 3B under ice-cooling, and then add 3.32 g of octyl chloride g. It was allowed to react at room temperature for 1 hour, and thereafter, the reaction solution was poured into ice water for oil-water separation. After the organic layer was washed 3 times with water, the solvent was removed, and the following intermediate 3C (1.1 g: yield 11%) was obtained through a silica gel column (ethyl acetate/hexane=1/10). [Chemical 54]
Figure 02_image125
(Step 3) Production of No. 190 The above-mentioned compound No. 190 was obtained in the same manner as in Step 4 of Example 1 except that the intermediate 1C was changed to the above-mentioned intermediate 3C. [Example 4] Production of Compound No. 191 The above-mentioned Compound No. 191. [Chemical 55]
Figure 02_image127
[Example 5] Production of Compound No. 192 The above-mentioned Compound No. 192. [Chemical 56]
Figure 02_image129
[Example 6] Production of Compound No. 193 (Step 1) Production of Intermediate 6B In the same manner as in Step 2 of Example 1, except that the indole compound 1A was changed to the following phenthiazine compound 6A Intermediate 6B described below was obtained. [Chemical 57]
Figure 02_image131
(Step 2) Production of intermediate 6C The intermediate 3B was changed to the above-mentioned intermediate 6B, and the equivalent of the reagent used was prepared in a manner that doubled the amount, except that it was the same as step 2 of Example 3. In this way, the following intermediate 6C was obtained. [Chemical 58]
Figure 02_image133
(Step 3) Production of intermediate 6D The intermediate 1B was changed to the above-mentioned intermediate 6C, and the equivalent of the reagent used was prepared in a manner that doubled the amount, except that it was the same as step 3 of Example 1. In this way, the following intermediate 6D was obtained. [Chemical 59]
Figure 02_image135
(Step 4) Production of Compound No. 193 The intermediate 1C was changed to the above-mentioned intermediate 6D, and the equivalent of the reagents used was prepared in such a way that the equivalent amount was doubled. In addition, the method was the same as in step 4 of Example 1. The above compound No.193 was obtained in the same manner. [Example 7] Production of Compound No. 194 (Step 1) Production of Intermediate 7A Except for changing Intermediate 1B to the above-mentioned Intermediate 6C, the following intermediate was obtained in the same manner as in Step 3 of Example 1 Object 7A. [Chemical 60]
Figure 02_image137
(Step 2)] Production of Compound No. 194 The above-mentioned Compound No. 194 was obtained in the same manner as in Step 4 of Example 1 except that Intermediate 1C was changed to the above-mentioned Intermediate 7A. The analysis results of the obtained compound Nos. 189 to 194 are shown in [Table 1] to [Table 3]. [Table 1]
Figure 107108827-A0304-0001
 [Table 2]
Figure 107108827-A0304-0002
 [table 3]
Figure 107108827-A0304-0003
 As apparent from the above [Table 1], the oxime ester compound of the present invention is useful because of its high solubility in solvents represented by PGMEA. [Manufacturing Example 1] Production of Blue Pigment Dispersion No.1 Using a bead mill, DISPERBYK-161 (12.5 parts by mass; manufactured by BYK-Chemie Japan) as a dispersant and Pigment Blue 15:6 (15 parts by mass) as a colorant parts by mass) were dispersed in PGMEA (72.5 parts by mass) to manufacture blue pigment dispersion liquid No.1. [Examples 8-14 and Comparative Example 1] Preparation of Photosensitive Compositions The components were mixed according to the composition of the following [Table 4] to obtain photosensitive compositions No. 1-No. 7 (Examples 8-14) And comparative photosensitive composition No.8 (comparative example 1). In addition, the number in a table shows a mass part. In Examples 8-14 and Comparative Example 1, the photoinitiator was used individually, respectively. In addition, the code|symbol in a table|surface represents the following component. A-1: Compound No.1 (the photopolymerization initiator of the present invention obtained in Example 1) A-2: Compound No.189 (the photopolymerization initiator of the present invention obtained in Example 2) A- 3: Compound No.190 (the photopolymerization initiator of the present invention obtained in Example 3) A-4: Compound No.191 (the photopolymerization initiator of the present invention obtained in Example 4) A-5: Compound No.192 (the photopolymerization initiator of the present invention obtained in Example 5) A-6: Compound No.193 (the photopolymerization initiator of the present invention obtained in Example 6) A-7: Compound No. .194 (the photopolymerization initiator of the present invention obtained in Example 7) A-8: OXE 02 (not belonging to the photopolymerization initiator of the present invention; manufactured by BASF Corporation) B-1: SPC-3000 (with acid Ethylenically unsaturated compound based on the base; manufactured by Showa Denko; PGMEA solution with solid content of 42.2% by mass) B-2: Kayarad DPHA (ethylenically unsaturated compound; manufactured by Nippon Kayaku; solid content of 100% by mass) C-1 : Blue pigment dispersion No.1 (the dispersion obtained in Production Example 1) X-1: KBE-403 (silane coupling agent; manufactured by Shin-Etsu Chemical) X-2: F-554 (fluorine-based leveling agent, containing Oligomers containing fluorine groups and lipophilic groups; manufactured by DIC) Y-1: PGMEA (solvent) Furthermore, SPC-3000 (B-1) is a compound with ethylenically unsaturated bonds and alkaline developability, Kayarad DPHA (B-2) is a compound with ethylenically unsaturated bonds but does not have alkaline developability. <Evaluation of photosensitive composition and cured product> The sensitivity of photosensitive composition No. 1 to No. 7 and comparative photosensitive composition No. 8 and the evaluation of the cured product obtained by using them were performed in the following order. evaluation of brightness. The evaluation results are also described in [Table 4]. (Sensitivity) Spin coating on a glass substrate (at 500 rpm for 2 seconds, then at 900 rpm for 5 seconds) photosensitive compositions No. 1 to No. 7 (Examples 8 to 14) and for comparison The photosensitive composition No.8 (comparative example 1) was pre-baked at 90° C. for 90 seconds using a hot plate, and then cooled at 23° C. for 40 seconds. Thereafter, exposure (exposure amount: 40 mJ/cm 2 ) was performed through a mask (mask opening: 30 μm) using a high-pressure mercury lamp. Development was performed using a 2.5% by mass sodium carbonate aqueous solution as a developer, followed by washing with water carefully, and post-baking in an oven at 230° C. for 30 minutes to fix the pattern. The obtained pattern was observed with an electron microscope, and the line width of the portion corresponding to the opening of the mask was measured. A line width of 30 μm or more was defined as A, and a line width of less than 30 μm was defined as B. The larger the line width, the better the sensitivity. (Brightness) Spin coating on a glass substrate (at 500 rpm for 2 seconds, then at 900 rpm for 5 seconds) of photosensitive compositions No. 1 to No. 7 (Examples 8 to 14) and for comparison The photosensitive composition No.8 (comparative example 1) was pre-baked at 90° C. for 90 seconds using a hot plate, and then cooled at 23° C. for 40 seconds. Thereafter, exposure was performed using a high-pressure mercury lamp at 100 mJ/cm 2 to prepare evaluation samples. Calculate the Y value according to JIS Z8701 based on the transmittance of the obtained sample at 380-780 nm. The higher the Y value, the higher the brightness, which means higher transmittance in the visible light region, which is useful. [Table 4]
Figure 107108827-A0304-0004
 From the above [Table 4], it is clear that the oxime ester compound of the present invention has higher sensitivity than the compound used in Comparative Example 1, and the cured product of the present invention has higher brightness. From the above, since the photosensitive composition using the oxime ester compound of the present invention is excellent in photolithography, and the brightness of the cured product obtained is excellent, it can be seen that the oxime ester compound of the present invention is useful as a photopolymerization initiator By. [Industrial Applicability] The oxime ester compound of the present invention is highly sensitive to efficiently generate free radicals for bright lines such as 365 nm (i-line), and can provide alkali-developable photosensitivity with excellent developability The resin composition also has high solubility in organic solvents and high transmittance in the visible light region, and is useful as a photopolymerization initiator used in photosensitive compositions.

Figure 107108827-A0101-11-0002-2
Figure 107108827-A0101-11-0002-2

Claims (11)

一種肟酯化合物，其以下述通式(Iα)或(Iβ)表示；
Figure 03_image139
(式中，R1 、R2 、R3 、R4 、R5 及R6 分別獨立地表示下述通式(II)所表示之基、氫原子、鹵素原子、硝基、氰基、羥基、羧基、R21 、OR21 、SR21 、NR22 R23 、COR21 、SOR21 、SO2 R21 或CONR22 R23 ； R1 、R2 、R3 、R4 、R5 及R6 中之至少一者為下述通式(II)所表示之基； R7 、R8 、R9 、R10 及R11 分別獨立地表示下述通式(IIIα)所表示之基、下述通式(IIIβ)所表示之基、氫原子、鹵素原子、硝基、氰基、羥基、羧基、R21 、OR21 、SR21 、NR22 R23 、COR21 、SOR21 、SO2 R21 或CONR22 R23 ； R7 、R8 、R9 、R10 及R11 中之至少一者為下述通式(IIIα)所表示之基或下述通式(IIIβ)所表示之基； R21 、R22 及R23 分別獨立地表示碳原子數1～20之烴基或碳原子數2～20之含雜環之基； R21 、R22 及R23 所表示之基中之氫原子有時被取代為鹵素原子、硝基、氰基、羥基、胺基、羧基、甲基丙烯醯基、丙烯醯基、環氧基、乙烯基、乙烯醚基、巰基、異氰酸基或含雜環之基，碳原子數2～20之烴基或碳原子數2～20之含雜環之基中之亞甲基有時被取代為-O-、-CO-、-COO-、-OCO-、-NR24 -、-NR24 CO-、-S-、-CS-、-SO2 -、-SCO-、-COS-、-OCS-或CSO-，R24 表示氫原子或碳原子數1～20之烴基； X1 表示不存在、直接鍵、-CO-、-O-或-S-； R1 與R2 、R2 與R3 、R3 與R4 、R5 與R6 、R6 與R7 、R7 與R8 、R8 與R9 、R9 與R10 、R10 與R11 、及R11 與R1 有時進行鍵結而形成環)，
Figure 03_image141
(式中，R31 及R32 分別獨立地表示氫原子、鹵素原子、硝基、氰基、碳原子數1～20之烴基或碳原子數2～20之含雜環之基； R31 及R32 所表示之碳原子數1～20之烴基或碳原子數2～20之含雜環之基之氫原子有時被取代為鹵素原子、硝基、氰基、羥基、胺基、羧基、甲基丙烯醯基、丙烯醯基、環氧基、乙烯基、乙烯醚基、巰基、異氰酸基或含雜環之基，R31 及R32 所表示之碳原子數2～20之烴基或碳原子數2～20之含雜環之基中之亞甲基有時被取代為-O-、-CO-、-COO-、-OCO-、-NR33 -、-NR33 CO-、-S-、-CS-、-SO2 -、-SCO-、-COS-、-OCS-或CSO-，R33 表示氫原子或碳原子數1～20之烴基； n表示0或1，*表示鍵結鍵)，
Figure 03_image143
(式中，R41 、R42 、R43 、R44 、R45 、R46 、R47 、R48 、R49 及R50 分別獨立地表示氫原子、鹵素原子、硝基、氰基、羥基、羧基、R51 、OR51 、SR51 、NR52 R53 、COR51 、SOR51 、SO2 R51 或CONR52 R53 ； R51 、R52 及R53 分別獨立地表示碳原子數1～20之烴基或碳原子數2～20之含雜環之基； R51 、R52 及R53 所表示之基中之氫原子有時被取代為鹵素原子、硝基、氰基、羥基、胺基、羧基、甲基丙烯醯基、丙烯醯基、環氧基、乙烯基、乙烯醚基、巰基、異氰酸基或含雜環之基，碳原子數2～20之烴基或碳原子數2～20之含雜環之基中之亞甲基有時被取代為-O-、-CO-、-COO-、-OCO-、-NR54 -、-NR54 CO-、-S-、-CS-、-SO2 -、-SCO-、-COS-、-OCS-或CSO-； X2 及X3 表示-O-、-S-或-NR54 -； R54 表示氫原子或碳原子數1～20之烴基； *表示鍵結鍵)，
Figure 03_image145
(式中，R101 、R102 、R103 、R104 、R105 、R106 、R107 及R108 分別獨立地表示上述通式(II)所表示之基、氫原子、鹵素原子、硝基、氰基、羥基、羧基、R121 、OR121 、SR121 、NR122 R123 、COR121 、SOR121 、SO2 R121 或CONR122 R123 ； R101 、R102 、R103 、R104 、R105 、R106 、R107 及R108 中之至少一者為上述通式(II)所表示之基； R109 、R110 、R111 、R112 及R113 分別獨立地表示上述通式(IIIα)所表示之基、上述通式(IIIβ)所表示之基、氫原子、鹵素原子、硝基、氰基、羥基、羧基、R121 、OR121 、SR121 、NR122 R123 、COR121 、SOR121 、SO2 R121 或CONR122 R123 ； R109 、R110 、R111 、R112 及R113 中之至少一者為下述通式(IIIα)所表示之基或下述通式(IIIβ)所表示之基； R121 、R122 及R123 分別獨立地表示碳原子數1～20之烴基或碳原子數2～20之含雜環之基； R121 、R122 及R123 所表示之基中之氫原子有時被取代為鹵素原子、硝基、氰基、羥基、胺基、羧基、甲基丙烯醯基、丙烯醯基、環氧基、乙烯基、乙烯醚基、巰基、異氰酸基或含雜環之基，碳原子數2～20之烴基或碳原子數2～20之含雜環之基中之亞甲基有時被取代為-O-、-CO-、-COO-、-OCO-、-NR124 -、-NR124 CO-、-S-、-CS-、-SO2 -、-SCO-、-COS-、-OCS-或CSO-； R124 表示氫原子或碳原子數1～20之烴基； X101 表示不存在、直接鍵、-CO-、-O-或-S-； R101 與R102 、R102 與R103 、R103 與R104 、R105 與R106 、R106 與R107 、R107 與R108 、R108 與R109 、R109 與R110 、R110 與R111 、R111 與R112 、R112 與R113 及R113 與R101 有時進行鍵結而形成環)。An oxime ester compound represented by the following general formula (Iα) or (Iβ);
Figure 03_image139
(In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently represent a group represented by the following general formula (II), a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group , carboxyl, R 21 , OR 21 , SR 21 , NR 22 R 23 , COR 21 , SOR 21 , SO 2 R 21 or CONR 22 R 23 ; R 1 , R 2 , R 3 , R 4 , R 5 and R 6 At least one of them is a group represented by the following general formula (II); R 7 , R 8 , R 9 , R 10 and R 11 each independently represent a group represented by the following general formula (IIIα), the following Group represented by general formula (IIIβ), hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, R 21 , OR 21 , SR 21 , NR 22 R 23 , COR 21 , SOR 21 , SO 2 R 21 or CONR 22 R 23 ; at least one of R 7 , R 8 , R 9 , R 10 and R 11 is a group represented by the following general formula (IIIα) or a group represented by the following general formula (IIIβ); R 21 , R 22 and R 23 independently represent a hydrocarbon group with 1 to 20 carbon atoms or a heterocyclic group with 2 to 20 carbon atoms; hydrogen atoms in the groups represented by R 21 , R 22 and R 23 Sometimes substituted by halogen atom, nitro group, cyano group, hydroxyl group, amine group, carboxyl group, methacryl group, acryl group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group or containing As a heterocyclic group, a hydrocarbon group with 2 to 20 carbon atoms or a heterocyclic group with 2 to 20 carbon atoms, the methylene group is sometimes substituted with -O-, -CO-, -COO-, -OCO -, -NR 24 -, -NR 24 CO-, -S-, -CS-, -SO 2 -, -SCO-, -COS-, -OCS- or CSO-, R 24 represents the number of hydrogen atoms or carbon atoms 1 to 20 hydrocarbon groups; X 1 represents absence, direct bond, -CO-, -O- or -S-; R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , R 9 and R 10 , R 10 and R 11 , and R 11 and R 1 are sometimes bonded to form a ring),
Figure 03_image141
(wherein, R 31 and R 32 independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group with 1 to 20 carbon atoms or a heterocyclic group with 2 to 20 carbon atoms; R 31 and The hydrogen atom of the hydrocarbon group with 1 to 20 carbon atoms or the heterocyclic group with 2 to 20 carbon atoms represented by R32 is sometimes substituted by a halogen atom, nitro, cyano, hydroxyl, amino, carboxyl, Methacryl group, acryl group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group or a group containing a heterocycle, a hydrocarbon group with 2 to 20 carbon atoms represented by R31 and R32 Or the methylene group in the heterocyclic ring-containing group with 2 to 20 carbon atoms may be substituted with -O-, -CO-, -COO-, -OCO-, -NR 33 -, -NR 33 CO-, -S-, -CS-, -SO 2 -, -SCO-, -COS-, -OCS- or CSO-, R 33 represents a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms; n represents 0 or 1, * represents a bonded key),
Figure 03_image143
(wherein, R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 and R 50 independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group , carboxyl, R 51 , OR 51 , SR 51 , NR 52 R 53 , COR 51 , SOR 51 , SO 2 R 51 or CONR 52 R 53 ; R 51 , R 52 and R 53 independently represent carbon atoms of 1 to A hydrocarbon group with 20 carbon atoms or a heterocyclic group with 2 to 20 carbon atoms; the hydrogen atoms in the groups represented by R 51 , R 52 and R 53 are sometimes substituted by halogen atoms, nitro groups, cyano groups, hydroxyl groups, and amines group, carboxyl group, methacryl group, acryl group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group or a group containing a heterocyclic ring, a hydrocarbon group with 2 to 20 carbon atoms or a carbon number The methylene group in the heterocycle-containing group of 2 to 20 is sometimes substituted by -O-, -CO-, -COO-, -OCO-, -NR 54 -, -NR 54 CO-, -S-, -CS-, -SO 2 -, -SCO-, -COS-, -OCS- or CSO-; X 2 and X 3 represent -O-, -S- or -NR 54 -; R 54 represents a hydrogen atom or carbon A hydrocarbon group with an atomic number of 1 to 20; * indicates a bond),
Figure 03_image145
(wherein, R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 and R 108 independently represent the group represented by the above general formula (II), hydrogen atom, halogen atom, nitro group , cyano, hydroxyl, carboxyl, R 121 , OR 121 , SR 121 , NR 122 R 123 , COR 121 , SOR 121 , SO 2 R 121 or CONR 122 R 123 ; R 101 , R 102 , R 103 , R 104 , At least one of R 105 , R 106 , R 107 and R 108 is a group represented by the above general formula (II); R 109 , R 110 , R 111 , R 112 and R 113 independently represent the above general formula ( A group represented by IIIα), a group represented by the above general formula (IIIβ), a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, R 121 , OR 121 , SR 121 , NR 122 R 123 , COR 121 , SOR 121 , SO 2 R 121 or CONR 122 R 123 ; at least one of R 109 , R 110 , R 111 , R 112 and R 113 is the group represented by the following general formula (IIIα) or the following general formula The group represented by (IIIβ); R 121 , R 122 and R 123 independently represent a hydrocarbon group with 1 to 20 carbon atoms or a heterocyclic group with 2 to 20 carbon atoms; R 121 , R 122 and R 123 The hydrogen atom in the group represented is sometimes replaced by a halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, methacryl group, acryl group, epoxy group, vinyl group, vinyl ether group, Mercapto, isocyanate or heterocyclic group, the methylene group in the hydrocarbon group with 2 to 20 carbon atoms or the heterocyclic group with 2 to 20 carbon atoms is sometimes substituted with -O-, -CO -, -COO-, -OCO-, -NR 124 -, -NR 124 CO-, -S-, -CS-, -SO 2 -, -SCO-, -COS-, -OCS- or CSO-; R 124 represents a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms; X 101 represents absence, direct bond, -CO-, -O- or -S-; R 101 and R 102 , R 102 and R 103 , R 103 and R 104 , R 105 and R 106 , R 106 and R 107 , R 107 and R 108 , R 108 and R 109 , R 109 and R 110 , R 110 and R 111 , R 111 and R 112 , R 112 and R 113 And R 113 and R 101 are sometimes bonded to form a ring). 如請求項1之肟酯化合物，其中通式(Iα)中之R3 及R5 中至少一者為通式(II)所表示之基。The oxime ester compound as claimed in item 1, wherein at least one of R 3 and R 5 in the general formula (Iα) is a group represented by the general formula (II). 如請求項1之肟酯化合物，其中通式(Iβ)中之R103 及R106 中至少一者為通式(II)所表示之基。The oxime ester compound as claimed in item 1, wherein at least one of R 103 and R 106 in general formula (Iβ) is a group represented by general formula (II). 如請求項1之肟酯化合物，其中通式(Iα)中之X1 不存在且R5 與R6 鍵結而形成苯環。The oxime ester compound as claimed in item 1, wherein X 1 in the general formula (Iα) does not exist and R 5 and R 6 are bonded to form a benzene ring. 一種光聚合起始劑，其含有如請求項1之肟酯化合物。A photopolymerization initiator, which contains the oxime ester compound as claimed in claim 1. 一種感光性組合物，其含有如請求項5之光聚合起始劑(A)及乙烯性不飽和化合物(B)。A photosensitive composition, which contains the photopolymerization initiator (A) and ethylenically unsaturated compound (B) as claimed in claim 5. 如請求項6之感光性組合物，其進而含有著色劑(C)。The photosensitive composition according to claim 6, which further contains a colorant (C). 一種鹼性顯影性感光性樹脂組合物，其係使如請求項6之感光性組合物含有鹼性顯影性化合物(D)而成。An alkali-developing photosensitive resin composition, which is formed by making the photosensitive composition according to claim 6 contain an alkali-developing compound (D). 一種硬化物，其係如請求項6之感光性組合物或如請求項8之鹼性顯影性感光性樹脂組合物之硬化物。A cured product, which is the cured product of the photosensitive composition according to Claim 6 or the alkali-developable photosensitive resin composition according to Claim 8. 一種顯示器顯示裝置，其含有如請求項9之硬化物。A display device comprising the cured product according to Claim 9. 一種硬化物之製造方法，其具有如下步驟：使用如請求項6之感光性組合物或如請求項8之鹼性顯影性感光性樹脂組合物，使該組合物硬化。A method for producing a cured product, comprising the steps of: using the photosensitive composition according to claim 6 or the alkali-developable photosensitive resin composition according to claim 8, and curing the composition.
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JP2017008219A (en) * 2015-06-23 2017-01-12 株式会社Adeka Composition

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