TWI476517B - Coloring the photosensitive resin composition - Google Patents

Coloring the photosensitive resin composition Download PDF

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TWI476517B
TWI476517B TW100104963A TW100104963A TWI476517B TW I476517 B TWI476517 B TW I476517B TW 100104963 A TW100104963 A TW 100104963A TW 100104963 A TW100104963 A TW 100104963A TW I476517 B TWI476517 B TW I476517B
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hydrogen atom
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TW201142495A (en
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Yuji Akiyama
yasuki Tatsumi
Soyeon Park
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Sumitomo Chemical Co
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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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/04—Azo compounds in general
    • C09B45/10—Cobalt compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists

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  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)

Description

著色感光性樹脂組合物Colored photosensitive resin composition

本發明係關於一種著色感光性樹脂組合物。The present invention relates to a colored photosensitive resin composition.

對於形成彩色濾光片之紅色像素之著色感光性樹脂組合物而言，為提高彩色濾光片之對比度，已知有使用染料作為著色感光性樹脂組合物中之著色劑。例如專利文獻1中記載有含有Orasol Red G作為紅色染料之著色感光性樹脂組合物。In order to improve the contrast of the color filter, it is known to use a dye as a coloring agent in the colored photosensitive resin composition for the colored photosensitive resin composition which forms the red pixel of the color filter. For example, Patent Document 1 describes a colored photosensitive resin composition containing Orasol Red G as a red dye.

[專利文獻1]日本專利特開2009-163226號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-163226

本發明之目的在於提供一種可獲得耐溶劑性更高之著色硬化物(例如著色塗膜、著色圖案)及含有其之彩色濾光片的著色感光性樹脂組合物。An object of the present invention is to provide a colored photosensitive resin composition which can obtain a colored cured product having a higher solvent resistance (for example, a colored coating film or a colored pattern) and a color filter containing the colored filter.

本發明提供以下[1]~[9]之發明。The present invention provides the following inventions [1] to [9].

[1]一種著色感光性樹脂組合物，其含有著色劑、樹脂、光聚合性化合物、光聚合起始劑及溶劑，且著色劑係包含有式(1)所示化合物者，[1] A colored photosensitive resin composition containing a colorant, a resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and the colorant contains a compound represented by the formula (1).

[式(1)中，R1 ~R18 彼此獨立表示氫原子、鹵素原子、碳數1~8之1價脂肪族烴基、硝基、-SO2 R29 或-SO2 R32 ；R29 表示-OH或-NHR30 ；R30 表示氫原子、碳數1~8之1價脂肪族烴基、可經碳數1~4之烷基取代之環己基、-R31 -O-R32 、-R31 -CO-O-R32 、-R31 -O-CO-R32 或碳數7~10之芳烷基；R31 表示碳數1~8之2價脂肪族烴基；R32 表示碳數1~8之1價脂肪族烴基；R19 及R20 彼此獨立表示氫原子、甲基、乙基或胺基；M1 表示Cr或Co；R21 ~R24 彼此獨立表示氫原子、碳數1~8之1價脂肪族烴基或碳數6~10之1價芳香族烴基，該脂肪族烴基及該芳香族烴基所含之氫原子可經羥基、-OR32 、磺基、-SO3 Na、-SO3 K或鹵素原子取代；R25 及R26 分別獨立表示氫原子或甲基；R27 表示伸乙基、丙烷-1,3-二基或丙烷-1,2-二基；R28 表示氫原子或碳數1~4之烷基；n表示1~4之整數；於n為2以上之整數時，複數個R27 可彼此相同亦可不同]。[In the formula (1), R 1 to R 18 each independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, -SO 2 R 29 or -SO 2 R 32 ; R 29 Represents -OH or -NHR 30 ; R 30 represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, -R 31 -OR 32 , -R 31 -CO-OR 32 , -R 31 -O-CO-R 32 or an aralkyl group having 7 to 10 carbon atoms; R 31 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms; and R 32 represents a carbon number of 1~ a monovalent aliphatic hydrocarbon group of 8; R 19 and R 20 independently represent a hydrogen atom, a methyl group, an ethyl group or an amine group; M 1 represents Cr or Co; and R 21 to R 24 independently represent a hydrogen atom and a carbon number of 1 to 2; a monovalent aliphatic hydrocarbon group of 8 or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, wherein the aliphatic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may pass through a hydroxyl group, -OR 32 , a sulfo group, -SO 3 Na, -SO 3 K or a halogen atom; R 25 and R 26 each independently represent a hydrogen atom or a methyl group; R 27 represents stretch ethyl, propane-1,3-diyl or propane-1,2-diyl; R 28 It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms of; n represents an integer of 1 to 4; when n is an integer of at least 2, the plural R 27 may be identical to one another also Different].

[2]如[1]之著色感光性組合物，其中著色劑係進而包含顏料者。[2] The colored photosensitive composition according to [1], wherein the colorant further contains a pigment.

[3]如[2]之著色感光性樹脂組合物，其中顏料為選自由C.I.顏料黃138、C.I.顏料黃139、C.I.顏料黃150、C.I.顏料紅177、C.I.顏料紅242及C.I.顏料紅254所組成之群中之至少一種。[3] The colored photosensitive resin composition according to [2], wherein the pigment is selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Red 177, CI Pigment Red 242, and CI Pigment Red 254. At least one of the group consisting of.

[4]如[1]至[3]中任一項之著色感光性樹脂組合物，其中樹脂為含有以下共聚物之樹脂，該共聚物具有來源於具有碳數2~4之環狀醚及乙烯性不飽和雙鍵的單體之結構單元、以及來源於選自由不飽和羧酸及不飽和羧酸酐所組成之群中的至少一種之結構單元。[4] The colored photosensitive resin composition according to any one of [1] to [3] wherein the resin is a resin containing a copolymer having a cyclic ether having a carbon number of 2 to 4 and A structural unit of a monomer having an ethylenically unsaturated double bond, and a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride.

[5]一種著色圖案，其係使用如[1]至[4]中任一項之著色感光性樹脂組合物而形成。[5] A colored pattern formed by using the colored photosensitive resin composition according to any one of [1] to [4].

[6]一種彩色濾光片，其含有如[5]之著色圖案。[6] A color filter containing a colored pattern as in [5].

[7]一種以式(2)所示之化合物，[7] a compound represented by formula (2),

[式(2)中，R1 ~R18 彼此獨立表示氫原子、鹵素原子、碳數1~8之1價脂肪族烴基、硝基、-SO2 R29 或-SO2 R32 ；R29 表示-OH或-NHR30 ；R30 表示氫原子、碳數1~8之1價脂肪族烴基、可經碳數1~4之烷基取代之環己基、-R31 -O-R32 、-R31 -CO-O-R32 、-R31 -O-CO-R32 或碳數7~10之芳烷基；R31 表示碳數1~8之2價脂肪族烴基；R32 表示碳數1~8之1價脂肪族烴基；R19 及R20 彼此獨立表示氫原子、甲基、乙基或胺基；M1 表示Cr或Co；R21 ~R24 彼此獨立表示氫原子、碳數1~8之1價脂肪族烴基或碳數6~10之1價芳香族烴基，該脂肪族烴基及該芳香族烴基所含之氫原子可經羥基、-OR32 、磺基、-SO3 Na、-SO3 K或鹵素原子取代；R25 及R26 分別獨立表示氫原子或甲基]。[In the formula (2), R 1 to R 18 each independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, -SO 2 R 29 or -SO 2 R 32 ; R 29 ; Represents -OH or -NHR 30 ; R 30 represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, -R 31 -OR 32 , -R 31 -CO-OR 32 , -R 31 -O-CO-R 32 or an aralkyl group having 7 to 10 carbon atoms; R 31 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms; and R 32 represents a carbon number of 1~ a monovalent aliphatic hydrocarbon group of 8; R 19 and R 20 independently represent a hydrogen atom, a methyl group, an ethyl group or an amine group; M 1 represents Cr or Co; and R 21 to R 24 independently represent a hydrogen atom and a carbon number of 1 to 2; a monovalent aliphatic hydrocarbon group of 8 or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, wherein the aliphatic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may pass through a hydroxyl group, -OR 32 , a sulfo group, -SO 3 Na, -SO 3 K or a halogen atom; R 25 and R 26 each independently represent a hydrogen atom or a methyl group].

[8]如[7]之化合物，其中M1 為Cr。[8] The compound according to [7], wherein M 1 is Cr.

[9]如[7]或[8]之化合物，其中R1 ~R18 中至少一個為硝基。[9] The compound according to [7] or [8], wherein at least one of R 1 to R 18 is a nitro group.

本發明之著色感光性樹脂組合物含有著色劑(A)、鹼溶性樹脂(B)、光聚合性化合物(C)、光聚合起始劑(D)及溶劑(E)，且著色劑(A)係包含式(1)所示化合物(以下有時稱為「化合物(1)」)者。The colored photosensitive resin composition of the present invention contains a coloring agent (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), and a coloring agent (A) The compound represented by the formula (1) (hereinafter sometimes referred to as "compound (1)") is included.

化合物(1)為鉻錯陰離子或鈷錯陰離子與來源於二苯并吡喃化合物之陽離子之鹽。The compound (1) is a salt of a chromium cation anion or a cobalt cation anion and a cation derived from a dibenzopyran compound.

[式(1)中，R1 ~R18 彼此獨立表示氫原子、鹵素原子、碳數1~8之1價脂肪族烴基、硝基、-SO2 R29 或-SO2 R32 。In the formula (1), R 1 to R 18 each independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, -SO 2 R 29 or -SO 2 R 32 .

R29 表示-OH或-NHR30 。R 29 represents -OH or -NHR 30 .

R30 表示氫原子、碳數1~8之1價脂肪族烴基、可經碳數1~4之烷基取代之環己基、-R31 -O-R32 、-R31 -CO-O-R32 、-R31 -O-CO-R32 或碳數7~10之芳烷基。R 30 represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, -R 31 -OR 32 , -R 31 -CO-OR 32 , R 31 -O-CO-R 32 or an aralkyl group having 7 to 10 carbon atoms.

R31 表示碳數1~8之2價脂肪族烴基。R 31 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

R32 表示碳數1~8之1價脂肪族烴基。R 32 represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

R19 及R20 彼此獨立表示氫原子、甲基、乙基或胺基。R 19 and R 20 independently of each other represent a hydrogen atom, a methyl group, an ethyl group or an amine group.

M1 表示Cr或Co。M 1 represents Cr or Co.

R21 ~R24 彼此獨立表示氫原子、碳數1~8之1價脂肪族烴基或碳數6~10之1價芳香族烴基，該脂肪族烴基及該芳香族烴基所含之氫原子可經羥基、-OR32 、磺基、-SO3 Na、-SO3 K或鹵素原子取代。R 21 to R 24 independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the aliphatic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may be Substituted by a hydroxyl group, -OR 32 , sulfo group, -SO 3 Na, -SO 3 K or a halogen atom.

R25 及R26 分別獨立表示氫原子或甲基。R 25 and R 26 each independently represent a hydrogen atom or a methyl group.

R27 表示伸乙基、丙烷-1,3-二基或丙烷-1,2-二基。R 27 represents an ethyl group, a propane-1,3-diyl group or a propane-1,2-diyl group.

R28 表示氫原子或碳數1~4之烷基。R 28 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

n表示1~4之整數。於n為2以上之整數時，複數個R27 可彼此相同亦可不同]。n represents an integer from 1 to 4. When n is an integer of 2 or more, the plurality of R 27 may be the same or different from each other].

作為碳數1~8之1價脂肪族烴基，可列舉甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、正戊基、正己基、正庚基、正辛基、癸基、1-甲基丁基、1,1,3,3-四甲基丁基、1,5-二甲基己基、1,6-二甲基庚基、2-乙基己基及1,1,5,5-四甲基己基等。Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, a t-butyl group, a n-pentyl group, and a n-hexyl group. N-heptyl, n-octyl, decyl, 1-methylbutyl, 1,1,3,3-tetramethylbutyl, 1,5-dimethylhexyl, 1,6-dimethylheptyl , 2-ethylhexyl and 1,1,5,5-tetramethylhexyl and the like.

作為碳數1~4之烷基，可列舉甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基等。Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a second butyl group, and a third butyl group.

作為碳數1~8之2價脂肪族烴基，可列舉亞甲基、伸乙基、丙烷-1,3-二基、丙烷-1,2-二基、丁烷-1,4-二基、丁烷-1,3-二基、戊烷-1,5-二基、己烷-1,6-二基、庚烷-1,7-二基、辛烷-1,8-二基等。Examples of the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include a methylene group, an exoethyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, and a butane-1,4-diyl group. Butane-1,3-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl Wait.

作為碳數6~10之1價芳香族烴基，可列舉：苯基、甲基苯基、二甲基苯基、三甲基苯基、乙基苯基、丙基苯基、丁基苯基、萘基等芳基；苄基、二苯基甲基、苯基乙基、3-苯基丙基等芳烷基等。Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, and a butylphenyl group. An aryl group such as a naphthyl group; an aralkyl group such as a benzyl group, a diphenylmethyl group, a phenylethyl group or a 3-phenylpropyl group.

作為可經碳數1~4之烷基取代之環己基，可列舉2-甲基環己基、2-乙基環己基、2-丙基環己基、2-異丙基環己基、2-丁基環己基、4-甲基環己基、4-乙基環己基、4-丙基環己基、4-異丙基環己基、4-丁基環己基等。Examples of the cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms include 2-methylcyclohexyl group, 2-ethylcyclohexyl group, 2-propylcyclohexyl group, 2-isopropylcyclohexyl group, and 2-butyl group. Alkylcyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-propylcyclohexyl, 4-isopropylcyclohexyl, 4-butylcyclohexyl, and the like.

作為-R31 -O-R32 ，可列舉甲氧基甲基、乙氧基甲基、丙氧基甲基、甲氧基乙基、乙氧基乙基、丙氧基乙基、甲氧基丙基、乙氧基丙基、丙氧基丙基、2-氧代-4-甲氧基丁基、辛氧基丙基、3-乙氧基丙基、3-(2-乙基己氧基)丙基等。Examples of -R 31 -OR 32 include methoxymethyl, ethoxymethyl, propoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxypropyl. , ethoxypropyl, propoxypropyl, 2-oxo-4-methoxybutyl, octyloxypropyl, 3-ethoxypropyl, 3-(2-ethylhexyloxy) Base) propyl and the like.

作為-R31 -CO-O-R32 ，可列舉甲氧基羰基甲基、甲氧基羰基乙基、乙氧基羰基甲基、乙氧基羰基乙基、丙氧基羰基甲基、丙氧基羰基乙基、丁氧基羰基甲基、丁氧基羰基乙基等。Examples of the -R 31 -CO-OR 32 include a methoxycarbonylmethyl group, a methoxycarbonylethyl group, an ethoxycarbonylmethyl group, an ethoxycarbonylethyl group, a propoxycarbonylmethyl group, and a propoxy group. Carbonylethyl, butoxycarbonylmethyl, butoxycarbonylethyl and the like.

作為-R31 -O-CO-R32 ，可列舉乙醯氧基甲基、乙醯氧基乙基、乙基羰氧基甲基、乙基羰氧基乙基、丙基羰氧基甲基、丙基羰氧基乙基、丁基羰氧基甲基、丁基羰氧基乙基等。Examples of -R 31 -O-CO-R 32 include etidyloxymethyl, ethoxylated ethyl, ethylcarbonyloxymethyl, ethylcarbonyloxyethyl, propylcarbonyloxymethyl. Base, propylcarbonyloxyethyl, butylcarbonyloxymethyl, butylcarbonyloxyethyl and the like.

作為-SO2 R29 ，可列舉：磺基；胺磺醯基；N-甲基胺磺醯基、N-乙基胺磺醯基、N-丙基胺磺醯基、N-異丙基胺磺醯基、N-丁基胺磺醯基、N-異丁基胺磺醯基、N-第二丁基胺磺醯基、N-第三丁基胺磺醯基、N-戊基胺磺醯基、N-(1-乙基丙基)胺磺醯基、N-(1,1-二甲基丙基)胺磺醯基、N-(1,2-二甲基丙基)胺磺醯基、N-(2,2-二甲基丙基)胺磺醯基、N-(1-甲基丁基)胺磺醯基、N-(2-甲基丁基)胺磺醯基、N-(3-甲基丁基)胺磺醯基、N-環戊基胺磺醯基、N-己基胺磺醯基、N-(1,3-二甲基丁基)胺磺醯基、N-(3,3-二甲基丁基)胺磺醯基、N-庚基胺磺醯基、N-(1-甲基己基)胺磺醯基、N-(1,4-二甲基戊基)胺磺醯基、N-辛基胺磺醯基、N-(2-乙基己基)胺磺醯基、N-(1,5-二甲基)己基胺磺醯基、N-(1,1,2,2-四甲基丁基)胺磺醯基、N-烯丙基胺磺醯基等經脂肪族烴基取代之胺磺醯基；N-(2-甲氧基乙基)胺磺醯基、N-(2-乙氧基乙基)胺磺醯基、N-(1-甲氧基丙基)胺磺醯基、N-(3-甲氧基丙基)胺磺醯基、N-(3-乙氧基丙基)胺磺醯基、N-(3-丙氧基丙基)胺磺醯基、N-(3-異丙氧基丙基)胺磺醯基、N-(3-己氧基丙基)胺磺醯基、N-(2-乙基己氧基丙基)胺磺醯基、N-(3-第三丁氧基丙基)胺磺醯基、N-(4-辛氧基丁基)胺磺醯基等經-R31 -O-R32 取代之胺磺醯基；N-(甲氧基羰基甲基)胺磺醯基、N-(甲氧基羰基乙基)胺磺醯基、N-(乙氧基羰基甲基)胺磺醯基、N-(乙氧基羰基乙基)胺磺醯基、N-(丙氧基羰基甲基)胺磺醯基、N-(丙氧基羰基乙基)胺磺醯基、N-(丁氧基羰基甲基)胺磺醯基、N-(丁氧基羰基乙基)胺磺醯基等經-R31 -CO-O-R32 取代之胺磺醯基；N-(乙醯氧基甲基)胺磺醯基、N-(乙醯氧基乙基)胺磺醯基、N-(乙基羰氧基甲基)胺磺醯基、N-(乙基羰氧基乙基)胺磺醯基、N-(丙基羰氧基甲基)胺磺醯基、N-(丙基羰氧基乙基)胺磺醯基、N-(丁基羰氧基甲基)胺磺醯基、N-(丁基羰氧基乙基)胺磺醯基等經-R31 -O-CO-R32 取代之胺磺醯基；N-環己基胺磺醯基、N-(2-甲基環己基)胺磺醯基、N-(3-甲基環己基)胺磺醯基、N-(4-甲基環己基)胺磺醯基、N-(4-丁基環己基)胺磺醯基等經具有取代基之環己基取代之胺磺醯基；N-苄基胺磺醯基、N-(1-苯基乙基)胺磺醯基、N-(2-苯基乙基)胺磺醯基、N-(3-苯基丙基)胺磺醯基、N-(4-苯基丁基)胺磺醯基、N-[2-(2-萘基)乙基]胺磺醯基、N-[2-(4-甲基苯基)乙基]胺磺醯基、N-(3-苯基-1-丙基)胺磺醯基、N-(3-苯基-1-甲基丙基)胺磺醯基等經芳烷基取代之胺磺醯基等。As -SO 2 R 29 , a sulfo group; an amine sulfonyl group; an N-methylamine sulfonyl group, an N-ethylamine sulfonyl group, an N-propylamine sulfonyl group, and an N-isopropyl group are mentioned. Aminesulfonyl, N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-tert-butylamine sulfonyl, N-tert-butylamine sulfonyl, N-pentyl Aminesulfonyl, N-(1-ethylpropyl)aminesulfonyl, N-(1,1-dimethylpropyl)aminesulfonyl, N-(1,2-dimethylpropyl Aminesulfonyl, N-(2,2-dimethylpropyl)aminesulfonyl, N-(1-methylbutyl)aminesulfonyl, N-(2-methylbutyl)amine Sulfonyl, N-(3-methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, N-hexylamine sulfonyl, N-(1,3-dimethylbutyl) Aminesulfonyl, N-(3,3-dimethylbutyl)aminesulfonyl, N-heptylaminesulfonyl, N-(1-methylhexyl)aminesulfonyl, N-(1 ,4-dimethylpentyl)amine sulfonyl, N-octylamine sulfonyl, N-(2-ethylhexyl)amine sulfonyl, N-(1,5-dimethyl)hexylamine a sulfonyl group, an N-(1,1,2,2-tetramethylbutyl)amine sulfonyl group, an N-allylamine sulfonyl group, an aminesulfonyl group substituted with an aliphatic hydrocarbon group; N-( 2-methoxyethyl)amine sulfonyl, N-(2-ethoxy Ethyl)sulfonyl, N-(1-methoxypropyl)aminesulfonyl, N-(3-methoxypropyl)aminesulfonyl, N-(3-ethoxypropyl Aminesulfonyl, N-(3-propoxypropyl)aminesulfonyl, N-(3-isopropoxypropyl)aminesulfonyl, N-(3-hexyloxypropyl) Aminesulfonyl, N-(2-ethylhexyloxypropyl)amine sulfonyl, N-(3-tert-butoxypropyl)amine sulfonyl, N-(4-octyloxy Aminesulfonyl group substituted by -R 31 -OR 32 ; N-(methoxycarbonylmethyl)amine sulfonyl, N-(methoxycarbonylethyl)amine sulfonyl , N-(ethoxycarbonylmethyl)amine sulfonyl, N-(ethoxycarbonylethyl)amine sulfonyl, N-(propoxycarbonylmethyl)amine sulfonyl, N-(propyl -R 31 -CO-OR 32 , such as oxycarbonylethyl)amine sulfonyl, N-(butoxycarbonylmethyl)amine sulfonyl, N-(butoxycarbonylethyl)amine sulfonyl Substituted aminoxime; N-(ethyloxymethyl)amine sulfonyl, N-(ethyloxyethyl)amine sulfonyl, N-(ethylcarbonyloxymethyl)amine sulfonate Mercapto, N-(ethylcarbonyloxyethyl)amine sulfonyl, N-(propylcarbonyloxymethyl)amine sulfonyl, N-(propylcarbonyloxyethyl)amine sulfonyl , N-( Ylcarbonyloxy methyl) acyl amine sulfonamide, N- (butylcarbonyloxy) amine and the like by sulfo acyl -R 31 -O-CO-R 32 of the amine sulfonamide substituted acyl; N-cyclohexyl Aminesulfonyl, N-(2-methylcyclohexyl)aminesulfonyl, N-(3-methylcyclohexyl)aminesulfonyl, N-(4-methylcyclohexyl)aminesulfonyl, N-(4-butylcyclohexyl)amine sulfonyl group, such as a sulfonyl group substituted with a cyclohexyl group having a substituent; N-benzylamine sulfonyl group, N-(1-phenylethyl)amine sulfonate Mercapto, N-(2-phenylethyl)amine sulfonyl, N-(3-phenylpropyl)amine sulfonyl, N-(4-phenylbutyl)amine sulfonyl, N- [2-(2-Naphthyl)ethyl]amine sulfonyl, N-[2-(4-methylphenyl)ethyl]amine sulfonyl, N-(3-phenyl-1-propyl An aminesulfonyl group substituted with an aralkyl group such as an aminesulfonyl group or an N-(3-phenyl-1-methylpropyl)aminesulfonyl group.

作為-SO2 R32 ，可列舉甲基磺醯基、乙基磺醯基、丙基磺醯基、異丙基磺醯基、正丁基磺醯基、第二丁基磺醯基、第三丁基磺醯基、戊基磺醯基、己基磺醯基、庚基磺醯基、辛基磺醯基、1-甲基丁基磺醯基、1,1,3,3-四甲基丁基磺醯基、1,5-二甲基己基磺醯基、1,6-二甲基庚基磺醯基、2-乙基己基磺醯基及1,1,5,5-四甲基己基磺醯基等。其中，較佳為甲基磺醯基及乙基磺醯基，更佳為甲基磺醯基。Examples of the -SO 2 R 32 include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a n-butylsulfonyl group, a second butylsulfonyl group, and a Tributylsulfonyl, pentylsulfonyl, hexylsulfonyl, heptylsulfonyl, octylsulfonyl, 1-methylbutylsulfonyl, 1,1,3,3-tetra Butyl sulfonyl, 1,5-dimethylhexylsulfonyl, 1,6-dimethylheptylsulfonyl, 2-ethylhexylsulfonyl and 1,1,5,5-tetra Methylhexylsulfonyl and the like. Among them, a methylsulfonyl group and an ethylsulfonyl group are preferred, and a methylsulfonyl group is more preferred.

較佳為R1 ~R18 中至少一個為硝基，其原因在於有耐熱性較高之傾向。It is preferred that at least one of R 1 to R 18 is a nitro group because of a tendency to have high heat resistance.

又，較佳為R1 ~R5 之至少一個及R6 ~R10 中至少一個為-SO2 R29 。於具有複數個-SO2 R29 時，複數個R29 可彼此相同亦可不同。Further, it is preferable that at least one of R 1 to R 5 and at least one of R 6 to R 10 are -SO 2 R 29 . When a plurality of -SO 2 R 29 are present, the plurality of R 29 may be the same or different from each other.

-SO2 R29 為-SO2 H或-SO2 NHR30 ，較佳為-SO2 NHR30 。其中較佳為氫原子或碳數1~8之1價脂肪族烴基，更佳為氫原子或2-乙基己基。-SO 2 R 29 is -SO 2 H or -SO 2 NHR 30 , preferably -SO 2 NHR 30 . Among them, a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms is preferable, and a hydrogen atom or a 2-ethylhexyl group is more preferable.

於本發明之化合物具有-SO2 R32 時，較佳為R11 ~R14 之至少一個及R15 ~R18 中至少一個為-SO2 R32 。於具有複數個-SO2 R32 時，複數個R32 可彼此相同亦可不同。When the compound of the present invention has -SO 2 R 32 , it is preferably at least one of R 11 to R 14 and at least one of R 15 to R 18 is -SO 2 R 32 . When having a plurality of -SO 2 R 32 , the plurality of R 32 may be the same or different from each other.

R21 ~R24 較佳為氫原子或可具有取代基之碳數1~8之1價脂肪族烴基，更佳為氫原子或乙基，其原因在於色濃度變高。R 21 to R 24 are preferably a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, more preferably a hydrogen atom or an ethyl group, because the color density is high.

R27 較佳為伸乙基及丙烷-1,2-二基，更佳為伸乙基。R 27 is preferably an ethyl group and a propane-1,2-diyl group, more preferably an ethyl group.

R28 較佳為氫原子。R 28 is preferably a hydrogen atom.

n為1~4之整數，較佳為2~4之整數，更佳為3或4。n is an integer of 1 to 4, preferably an integer of 2 to 4, more preferably 3 or 4.

作為-(R27 -O)n-R28 ，較佳為2-(2-羥基乙氧基)乙基及2-[2-(2-羥基乙氧基)乙氧基]乙基，更佳為2-[2-(2-羥基乙氧基)乙氧基]乙基，其原因在於存在化合物(1)於有機溶劑中之溶解性提高之傾向。And -(R 27 -O)nR 28 , preferably 2-(2-hydroxyethoxy)ethyl and 2-[2-(2-hydroxyethoxy)ethoxy]ethyl, more preferably 2-[2-(2-hydroxyethoxy)ethoxy]ethyl is due to the tendency of the solubility of the compound (1) in an organic solvent to be improved.

化合物(1)中，作為成為錯陰離子之配位基的吡唑偶氮化合物之較佳例，可列舉式(1-a1)~式(1-a64)所示化合物等。In the compound (1), preferred examples of the pyrazole azo compound which is a ligand which is a substituent of the wrong anion include a compound represented by the formula (1-a1) to the formula (1-a64).

化合物(1)中，作為錯陰離子之較佳例，可列舉式(1-b1)~式(1-b60)所示陰離子等。In the compound (1), preferred examples of the wrong anion include an anion represented by the formula (1-b1) to the formula (1-b60).

化合物(1)中，作為來源於二苯并吡喃化合物之陽離子之較佳例，可列舉式(1-c1)~式(1-c48)所示陽離子等。In the compound (1), examples of the cation derived from the dibenzopyran compound include a cation represented by the formula (1-c1) to the formula (1-c48).

化合物(1)可藉由以下方式製造：使用式(1d)所示化合物(以下有時稱為「化合物(1d)」)與鉻化合物形成鉻錯鹽，然後使該鉻錯鹽與二苯并吡喃化合物進行鹽交換反應；或使用化合物(1d)與鈷化合物形成鈷錯鹽，然後使該鈷錯鹽與二苯并吡喃化合物(b)進行鹽交換反應。The compound (1) can be produced by forming a chromium salt with a chromium compound using a compound represented by the formula (1d) (hereinafter sometimes referred to as "compound (1d)"), and then making the chromium salt and dibenzo The pyran compound is subjected to a salt exchange reaction; or the compound (1d) is used to form a cobalt salt with a cobalt compound, and then the cobalt salt is subjected to a salt exchange reaction with the dibenzopyran compound (b).

[式(a4)中，R1 ~R5 、R11 ~R14 及R19 表示與式(1)中者相同之含意][In the formula (a4), R 1 to R 5 , R 11 to R 14 and R 19 represent the same meanings as in the formula (1)]

[式(b)中、R21 ~R28 及n表示與式(1)中者相同之含意。A- 表示1價陰離子][In the formula (b), R 21 to R 28 and n represent the same meanings as those in the formula (1). A - represents a monovalent anion]

1價陰離子可列舉Cl- 、Br- 、I- 、ClO4 - 、PF6 - 或BF4 - 等。Examples of the monovalent anion include Cl - , Br - , I - , ClO 4 - , PF 6 - or BF 4 - .

二苯并吡喃化合物(b)可藉由使式(b0)所示化合物與式(b1)所示化合物於有機溶劑中反應而製造。The dibenzopyran compound (b) can be produced by reacting a compound represented by the formula (b0) with a compound represented by the formula (b1) in an organic solvent.

[式(b0)及式(b1)中，R21 ~R28 及n表示與式(1)中者相同之含意。A- 表示與式(b)中者相同之含意][In the formula (b0) and the formula (b1), R 21 to R 28 and n represent the same meanings as those in the formula (1). A - indicates the same meaning as in the formula (b)]

上述反應中，反應溫度較佳為15℃~60℃，反應時間較佳為1小時~12小時。又，就反應時間縮短或產率提高之方面而言，較佳為使用酸觸媒及/或脫水劑。In the above reaction, the reaction temperature is preferably from 15 ° C to 60 ° C, and the reaction time is preferably from 1 hour to 12 hours. Further, in terms of shortening of the reaction time or improvement of the yield, it is preferred to use an acid catalyst and/or a dehydrating agent.

作為酸觸媒，可列舉硫酸、對甲苯磺酸等。Examples of the acid catalyst include sulfuric acid and p-toluenesulfonic acid.

作為脫水劑，可列舉：二環己基碳二醯亞胺、二異丙基碳二醯亞胺、1-乙基-3-(3-二甲基胺基丙基)碳二醯亞胺鹽酸鹽等碳二醯亞胺類；1-烷基-2-鹵代吡啶鎓鹽類；1,1'-羰基二咪唑；雙(2-氧代-3-唑啶基)次膦酸氯化物；二-2-吡啶基碳酸鹽等。其中，作為脫水劑，就後處理及純化容易之觀點而言，較佳為1-乙基-3-(3-二甲基胺基丙基)碳二醯亞胺鹽酸鹽。Examples of the dehydrating agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide salt. Carboxylides such as acid salts; 1-alkyl-2-halopyridinium salts; 1,1'-carbonyldiimidazole; bis(2-oxo-3- Pyrazinyl)phosphinic acid chloride; di-2-pyridyl carbonate and the like. Among them, as the dehydrating agent, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride is preferred from the viewpoint of ease of post-treatment and purification.

作為上述反應中使用之有機溶劑，可列舉二氯甲烷、氯仿、四氫呋喃、甲苯、乙腈等。Examples of the organic solvent used in the above reaction include dichloromethane, chloroform, tetrahydrofuran, toluene, and acetonitrile.

成為化合物(1)之錯陰離子之配位基的化合物(1d)係於染料領域中廣為人知，可藉由使重氮鎓鹽與吡唑化合物進行重氮偶合之方法而製造。例如可將藉由使用亞硝酸、亞硝酸鹽或亞硝酸酯將式(1a)所示胺(重氮成分)(以下有時稱為「胺(1a)」)重氮化所得之式(1b)所示化合物用作上述重氮鎓鹽。The compound (1d) which is a ligand of the wrong anion of the compound (1) is widely known in the field of dyes, and can be produced by a method in which a diazonium salt and a pyrazole compound are subjected to diazo coupling. For example, a formula (1b) obtained by diazotizing an amine (diazo component) represented by the formula (1a) (hereinafter sometimes referred to as "amine (1a)") by using nitrous acid, nitrite or nitrite can be used. The compound shown is used as the above diazonium salt.

[式(1a)及式(1b)中，R11 ~R14 表示與式(1)中者相同之含意。A1 表示無機或有機陰離子]In the formulae (1a) and (1b), R 11 to R 14 have the same meanings as those in the formula (1). A 1 represents an inorganic or organic anion]

作為上述無機陰離子，例如可列舉氟化物離子、氯化物離子、溴化物離子、碘化物離子、過氯酸根離子、次氯酸離子等。Examples of the inorganic anion include a fluoride ion, a chloride ion, a bromide ion, an iodide ion, a perchlorate ion, and a hypochlorous acid ion.

作為上述有機陰離子，例如可列舉CH3 COO- 、PhCOO- 等。Examples of the organic anion include CH 3 COO − , PhCOO − and the like.

較佳可列舉氯化物離子、溴化物離子、CH3 COO- 等。Preferred are chloride ions, bromide ions, CH 3 COO - and the like.

藉由使式(1b)所示化合物與式(1c)所示化合物於水性溶劑中進行重氮偶合，可製造式(1d)所示化合物(以下有時稱為「化合物(1d)」)。反應溫度較佳為-5℃~60℃，更佳為0℃~30℃。反應時間較佳為1小時~12小時，更佳為1小時~4小時。作為上述水性溶劑，例如可列舉N-甲基吡咯啶酮等。The compound represented by the formula (1b) can be produced by diazo coupling with a compound represented by the formula (1b) in an aqueous solvent (hereinafter sometimes referred to as "compound (1d)"). The reaction temperature is preferably -5 ° C to 60 ° C, more preferably 0 ° C to 30 ° C. The reaction time is preferably from 1 hour to 12 hours, more preferably from 1 hour to 4 hours. Examples of the aqueous solvent include N-methylpyrrolidone and the like.

[式(1c)中，R1 ~R5 及R19 表示與式(1)中者相同之含意]於化合物(1d)具有-SO2 R29 、且-SO2 R29 為-SO2 NHR30 時，亦可藉由使用具有-SO2 NHR30 之胺(1a)而製造，較佳為使用具有磺基之胺(1a)進行偶合反應後，將磺基加以磺醯胺化而製造。例如對於化合物(1d)，可預先合成具有磺基之偶氮化合物(以下稱為「化合物(1s)」)，藉由亞硫醯鹵化合物將磺基(-SO3 H)加以磺醯鹵化(-SO2 X，X為鹵素原子)而獲得磺醯鹵化合物，繼而使磺醯鹵化合物與胺(R30 NH2 )反應，藉此將磺基加以磺醯胺化而製造化合物(1d)。[In the formula (1c), R 1 to R 5 and R 19 represent the same meanings as in the formula (1)] wherein the compound (1d) has -SO 2 R 29 and -SO 2 R 29 is -SO 2 NHR At 30 o'clock, it can also be produced by using an amine (1a) having -SO 2 NHR 30 , preferably by a coupling reaction using an amine (1a) having a sulfo group, followed by sulfonylation of the sulfo group. For example, for the compound (1d), an azo compound having a sulfo group (hereinafter referred to as "compound (1s)") may be previously synthesized, and a sulfo group (-SO 3 H) may be halogenated by a sulfonium halide compound ( -SO 2 X, X is a halogen atom), a sulfonium halide compound is obtained, and then a sulfonium halide compound is reacted with an amine (R 30 NH 2 ), whereby a sulfo group is sulfonated to produce a compound (1d).

作為化合物(1s)之具體例，可列舉式(1-a1)、式(1-a2)、式(1-a5)~(1-a20)所示化合物，較佳可列舉式(1-a5)、(1-a6)、(1-a15)及(1-a16)所示化合物。作為亞硫醯鹵化合物，可列舉亞硫醯氟、亞硫醯氯、亞硫醯溴、亞硫醯碘等，較佳可列舉亞硫醯氯、亞硫醯溴等，特佳可列舉亞硫醯氯。亞硫醯鹵之使用量較佳為相對於化合物(1s)1莫耳而為1~10莫耳。再者，於反應體系中混入有水之情形時，較佳為過剩使用亞硫醯鹵化合物。Specific examples of the compound (1s) include compounds represented by the formula (1-a1), the formula (1-a2), and the formula (1-a5) to (1-a20), and preferably, the formula (1-a5) ), (1-a6), (1-a15) and (1-a16) compounds. Examples of the sulfinium halide compound include sulfinium fluoride, sulfinium chloride, sulfinium bromide, and sulfinium iodide. Preferred examples thereof include sulfinium chloride and sulfinium bromide. Thiopurine chloride. The amount of the sulfinium halide used is preferably from 1 to 10 moles per mole of the compound (1s). Further, when water is mixed in the reaction system, it is preferred to use a sulfoxide halogen compound excessively.

磺醯鹵化較佳為於溶劑中進行。作為溶劑，例如可列舉：1,4-二烷等醚類(特佳為環狀醚類)；氯仿、二氯甲烷、四氯化碳、1,2-二氯乙烷、二氯乙烯、三氯乙烯、全氯乙烯、二氯丙烷、氯戊烷、1,2-二溴乙烷等鹵化烴類等。溶劑之使用量相對於化合物(1s)1質量份而通常為3質量份以上，較佳為5質量份以上，且通常為10質量份以下，較佳為8質量份以下。又，磺醯鹵化時，較佳為併用N,N-二烷基甲醯胺(例如N,N-二甲基甲醯胺、N,N-二乙基甲醯胺等)。於使用N,N-二烷基甲醯胺之情形時，其使用量相對於亞硫醯鹵化合物1莫耳而通常為0.05~1莫耳。若將化合物(1s)與N,N-二烷基甲醯胺於溶劑中預先混合後添加亞硫醯鹵化合物，則可抑制發熱。The sulfonium halide is preferably carried out in a solvent. As a solvent, for example, 1,4-two Ethers such as alkanes (excellently cyclic ethers); chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, dichloroethylene, trichloroethylene, perchloroethylene, dichloropropane, Halogenated hydrocarbons such as chloropentane and 1,2-dibromoethane. The amount of the solvent to be used is usually 3 parts by mass or more, preferably 5 parts by mass or more, and usually 10 parts by mass or less, and preferably 8 parts by mass or less based on 1 part by mass of the compound (1s). Further, when the sulfonium is halogenated, N,N-dialkylformamide (for example, N,N-dimethylformamide, N,N-diethylformamide or the like) is preferably used in combination. In the case of using N,N-dialkylformamide, it is usually used in an amount of 0.05 to 1 mol per mol of the sulfonium halide compound. When the compound (1s) and N,N-dialkylformamide are premixed in a solvent and then a sulfoxide compound is added, heat generation can be suppressed.

磺醯鹵化時之反應溫度通常為0℃以上，較佳為30℃以上，且為70℃以下，較佳為60℃以下。反應時間例如為0.5小時以上，較佳為3小時以上，且通常為8小時以下，較佳為5小時以下。如上所述般製備之磺醯鹵化合物可單離後與胺(R30 NH2 )反應，亦可不加單離而保持反應混合物之狀態直接與胺(R30 NH2 )反應。再者，於單離之情形時，只要將反應混合物與水混合而濾取所析出之結晶即可。所取得之磺醯鹵化合物之結晶亦可於與胺(R30 NH2 )之反應前視需要進行水洗及乾燥。The reaction temperature at the time of halogenation of the sulfonium is usually 0 ° C or higher, preferably 30 ° C or higher, and 70 ° C or lower, preferably 60 ° C or lower. The reaction time is, for example, 0.5 hours or longer, preferably 3 hours or longer, and usually 8 hours or shorter, preferably 5 hours or shorter. The sulfonium halide compound prepared as described above may be reacted with an amine (R 30 NH 2 ) after isolation, or may be directly reacted with an amine (R 30 NH 2 ) while maintaining the reaction mixture without isolation. Further, in the case of isolation, the reaction mixture may be mixed with water to collect the precipitated crystals. The crystallization of the obtained sulfonium halide compound can also be washed with water and dried as needed before the reaction with the amine (R 30 NH 2 ).

作為胺(R30 NH2 )，包括正丙胺、正丁胺、正己胺、二甲基己基胺(1,5-二甲基己基胺等)、四甲基丁基胺(1,1,3,3-四甲基丁基胺等)、乙基己基胺(2-乙基己基胺等)、胺基苯基丁烷(3-胺基-1-苯基丁烷等)、異丙氧基丙基胺等。胺(R30 NH2 )之使用量相對於磺醯鹵化合物1莫耳而通常為2莫耳以上、10莫耳以下，較佳為2莫耳以上、7莫耳以下。磺醯鹵化合物與胺(R30 NH2 )之添加順序並無特別限定，較佳為於磺醯鹵化合物中添加(滴加)胺(R30 NH2 )。又，磺醯鹵化合物與胺(R30 NH2 )之反應較佳為於溶劑中進行。作為溶劑，可使用與製備磺醯鹵化合物時相同之溶劑。As an amine (R 30 NH 2 ), including n-propylamine, n-butylamine, n-hexylamine, dimethylhexylamine (1,5-dimethylhexylamine, etc.), tetramethylbutylamine (1,1,3) , 3-tetramethylbutylamine, etc.), ethylhexylamine (2-ethylhexylamine, etc.), aminophenylbutane (3-amino-1-phenylbutane, etc.), isopropoxy Alkylamine and the like. The amount of the amine (R 30 NH 2 ) used is usually 2 mol or more and 10 mol or less, preferably 2 mol or more and 7 mol or less, relative to the sulfonium halide compound 1 mol. The order of addition of the sulfonium halide compound and the amine (R 30 NH 2 ) is not particularly limited, and it is preferred to add (drop) an amine (R 30 NH 2 ) to the sulfonium halide compound. Further, the reaction of the sulfonium halide compound with an amine (R 30 NH 2 ) is preferably carried out in a solvent. As the solvent, the same solvent as that used in the preparation of the sulfonium halide compound can be used.

又，磺醯鹵化合物與胺(R30 NH2 )之反應較佳為於鹼性觸媒之存在下進行。作為鹼性觸媒，例如可列舉三級胺(三乙胺、三乙醇胺等脂肪族三級胺；吡啶等芳香族三級胺)及二級胺(二乙胺等脂肪族二級胺；哌啶等環狀脂肪族二級胺)等。該等中，較佳為三級胺，特佳為三乙胺等脂肪族三級胺。鹼性觸媒之使用量相對於胺(R30 NH2 )而通常為1.1莫耳以上、6莫耳以下，較佳為1.1莫耳以上、5莫耳以下。Further, the reaction of the sulfonium halide compound with an amine (R 30 NH 2 ) is preferably carried out in the presence of a basic catalyst. Examples of the basic catalyst include tertiary amines (aliphatic tertiary amines such as triethylamine and triethanolamine; aromatic tertiary amines such as pyridine) and secondary amines (aliphatic secondary amines such as diethylamine; A cyclic aliphatic secondary amine such as pyridine or the like. Among these, a tertiary amine is preferred, and an aliphatic tertiary amine such as triethylamine is particularly preferred. The amount of the basic catalyst used is usually 1.1 mol or more and 6 mol or less, preferably 1.1 mol or more and 5 mol or less, relative to the amine (R 30 NH 2 ).

於磺醯鹵化合物中添加胺(R30 NH2 )與鹼性觸媒時，鹼性觸媒之添加時序並無特別限定，胺(R30 NH2 )之添加前及添加後均可，亦可以與胺(R30 NH2 )相同之時序添加。又，亦可與反應性胺預先混合後添加，亦可與胺(R30 NH2 )分開而另行添加。When the amine (R 30 NH 2 ) and the basic catalyst are added to the sulfonium halide compound, the addition timing of the basic catalyst is not particularly limited, and the amine (R 30 NH 2 ) may be added before and after the addition. It can be added at the same timing as the amine (R 30 NH 2 ). Further, it may be added after mixing with a reactive amine, or may be added separately from the amine (R 30 NH 2 ).

磺醯鹵化合物與胺(R30 NH2 )之反應溫度通常為0℃以上、50℃以下，較佳為0℃以上、30℃以下。又，反應時間通常為1~5小時。The reaction temperature of the sulfonium halide compound and the amine (R 30 NH 2 ) is usually 0 ° C or higher and 50 ° C or lower, preferably 0 ° C or higher and 30 ° C or lower. Further, the reaction time is usually from 1 to 5 hours.

自反應混合物取得作為目標化合物之化合物(1d)之方法並無特別限定，可採用公知之各種方法。例如，較佳為將反應混合物與酸(例如乙酸等)及水一起混合，濾取所析出之結晶。關於上述酸，較佳為預先製備酸之水溶液後將反應混合物添加至上述水溶液中。添加反應混合物時之溫度通常為10℃以上、50℃以下，較佳為20℃以上、50℃以下，更佳為20℃以上、30℃以下。又，將反應混合物添加至酸之水溶液中後，較佳為於相同溫度下攪拌0.5~2小時左右。所濾取之結晶較佳為以水等清洗，繼而進行乾燥。又，視需要亦可藉由再結晶等公知方法進一步純化。The method of obtaining the compound (1d) as the target compound from the reaction mixture is not particularly limited, and various known methods can be employed. For example, it is preferred to mix the reaction mixture with an acid such as acetic acid or the like and water, and the precipitated crystals are collected by filtration. With respect to the above acid, it is preferred to add a reaction mixture to the above aqueous solution after preparing an aqueous acid solution in advance. The temperature at the time of adding the reaction mixture is usually 10 ° C or more and 50 ° C or less, preferably 20 ° C or more and 50 ° C or less, more preferably 20 ° C or more and 30 ° C or less. Further, after the reaction mixture is added to the aqueous acid solution, it is preferably stirred at the same temperature for about 0.5 to 2 hours. The crystals to be filtered are preferably washed with water or the like, followed by drying. Further, it may be further purified by a known method such as recrystallization, as needed.

於化合物(1)之陰離子部分為鉻錯陰離子(式(1)中之M1 為Cr)之情形時，可藉由使化合物(1d)與鉻化合物於水性溶劑中、通常於70~100℃下反應而製造。較佳為使化合物(1d)與鉻化合物以2：1~4：1之莫耳比反應。When the anion moiety of the compound (1) is a chromium cation anion (M 1 in the formula (1) is Cr), the compound (1d) and the chromium compound can be used in an aqueous solvent, usually at 70 to 100 ° C. Manufactured by the next reaction. It is preferred to react the compound (1d) with a chromium compound at a molar ratio of 2:1 to 4:1.

作為上述鉻化合物，可列舉甲酸鉻、乙酸鉻、氯化鉻、氟化鉻等，較佳可列舉甲酸鉻、乙酸鉻等。化合物(1)可藉由使鉻錯鹽與二苯并吡喃化合物(b)於溶劑中進行鹽交換反應而製造。較佳為使鉻錯鹽與二苯并吡喃化合物(b)以1：1~1：4之莫耳比反應。Examples of the chromium compound include chromium formate, chromium acetate, chromium chloride, and chromium fluoride. Preferred examples thereof include chromium formate and chromium acetate. The compound (1) can be produced by subjecting a chromium salt to a salt exchange reaction with a dibenzopyran compound (b) in a solvent. Preferably, the chromium salt is reacted with the dibenzopyran compound (b) at a molar ratio of 1:1 to 1:4.

於化合物(1)之陰離子部分為鈷錯陰離子(式(1)中之M1 為Co)之情形時，可藉由使化合物(1d)與鈷化合物於水性溶劑中、通常於70~100℃下反應而製造。較佳為使化合物(1d)與鈷化合物以2：1~4：1之莫耳比反應。作為上述鈷化合物，可列舉氯化鈷、乙酸鈷、硫酸鈷、三(2,4-戊二酮酸)鈷(III)等，較佳可列舉三(2,4-戊二酮酸)鈷(III)等。In the case where the anion moiety of the compound (1) is a cobalt cation anion (M 1 in the formula (1) is Co), the compound (1d) and the cobalt compound can be used in an aqueous solvent, usually at 70 to 100 ° C. Manufactured by the next reaction. It is preferred to react the compound (1d) with the cobalt compound at a molar ratio of 2:1 to 4:1. Examples of the cobalt compound include cobalt chloride, cobalt acetate, cobalt sulfate, and tris(2,4-pentanedionate) cobalt (III). Preferred examples thereof include tris(2,4-pentanedionate) cobalt. (III) and so on.

化合物(1)可藉由使鈷錯鹽與二苯并吡喃化合物(b)於溶劑中進行鹽交換反應而製造。較佳為使鈷錯鹽與二苯并吡喃化合物(b)以1：1~1：4之莫耳比反應。作為化合物(1)，具體可列舉式(1-1)~式(1-26)所示化合物等。The compound (1) can be produced by subjecting a cobalt salt to a salt exchange reaction with a dibenzopyran compound (b) in a solvent. Preferably, the cobalt salt is reacted with the dibenzopyran compound (b) at a molar ratio of 1:1 to 1:4. Specific examples of the compound (1) include a compound represented by the formula (1-1) to the formula (1-26).

化合物(1)中，就於有機溶劑中之溶解性較高之方面而言，較佳為式(2)所示化合物(以下有時稱為「化合物(2)」)。In the compound (1), the compound represented by the formula (2) (hereinafter sometimes referred to as "compound (2)") is preferred in terms of high solubility in an organic solvent.

[式(2)中、R1 ~R18 彼此獨立表示氫原子、鹵素原子、碳數1~8之1價脂肪族烴基、硝基、-SO2 R29 或-SO2 R32 。In the formula (2), R 1 to R 18 each independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, -SO 2 R 29 or -SO 2 R 32 .

R29 表示-OH或-NHR30 。R 29 represents -OH or -NHR 30 .

R30 表示氫原子、碳數1~8之1價脂肪族烴基、可經碳數1~4之烷基取代之環己基、-R31 -O-R32 、-R31 -CO-O-R32 、-R31 -O-CO-R32 或碳數7~10之芳烷基。R31 表示碳數1~8之2價脂肪族烴基。R32 表示碳數1~8之1價脂肪族烴基。R19 及R20 彼此獨立表示氫原子、甲基、乙基或胺基。M1 表示Cr或Co。R 30 represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, -R 31 -OR 32 , -R 31 -CO-OR 32 , R 31 -O-CO-R 32 or an aralkyl group having 7 to 10 carbon atoms. R 31 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms. R 32 represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms. R 19 and R 20 independently of each other represent a hydrogen atom, a methyl group, an ethyl group or an amine group. M 1 represents Cr or Co.

R21 ~R24 彼此獨立表示氫原子、碳數1~8之1價脂肪族烴基或碳數6~10之1價芳香族烴基，該脂肪族烴基及該芳香族烴基所含之氫原子可經羥基、-OR32 、磺基、-SO3 Na、-SO3 K或鹵素原子取代。R 21 to R 24 independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the aliphatic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may be Substituted by a hydroxyl group, -OR 32 , sulfo group, -SO 3 Na, -SO 3 K or a halogen atom.

R25 及R26 分別獨立表示氫原子或甲基]M1 較佳為Cr。又，較佳為R1 ~R18 中至少一個為硝基。藉由具有硝基，有耐熱性變高之傾向。較佳為R1 ~R5 之至少一個及R6 ~R10 中至少一個為-SO2 R29 ，其中，更佳為選自由-SO2 H(即R29 為-OH)及-SO2 NHR33 (即R29 為-NHR33 )所組成之群中之至少一種。於化合物(2)具有-SO2 R32 時，較佳為R11 ~R14 之至少一個及R15 ~R18 中至少一個為-SO2 R32 。R33 為氫原子或碳數1~8之1價脂肪族烴基。作為碳數1~8之1價脂肪族烴基，可列舉與上述所列舉者相同者。具有-SO2 R29 、且R29 為-NHR33 之化合物可利用除了將上述胺(R30 NH2 )換成胺(R33 NH2 )以外與化合物(1)相同之方法製造。R 25 and R 26 each independently represent a hydrogen atom or a methyl group. M 1 is preferably Cr. Further, it is preferred that at least one of R 1 to R 18 is a nitro group. By having a nitro group, heat resistance tends to be high. Preferably, at least one of R 1 to R 5 and at least one of R 6 to R 10 are -SO 2 R 29 , wherein more preferably selected from -SO 2 H (ie, R 29 is -OH) and -SO 2 At least one of the group consisting of NHR 33 (ie, R 29 is -NHR 33 ). When the compound (2) has -SO 2 R 32 , at least one of R 11 to R 14 and at least one of R 15 to R 18 are -SO 2 R 32 . R 33 is a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms. Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms are the same as those recited above. A compound having -SO 2 R 29 and R 29 is -NHR 33 can be produced by the same method as the compound (1) except that the above amine (R 30 NH 2 ) is replaced with an amine (R 33 NH 2 ).

作為化合物(2)之具體例，可列舉式(1-1)、式(1-3)~式(1-5)、式(1-7)~式(1-9)、式(1-11)~式(1-16)、式(1-18)~式(1-21)及式(1-23)~式(1-26)所示化合物，其中，較佳為式(1-1)~式(1-3)、式(1-21)及式(1-23)~式(1-26)所示化合物。化合物(1)之含量於著色劑(A)中較佳為1質量%以上、99質量%以下，更佳為1質量%以上、80質量%以下，進而佳為3質量%以上、70質量%以下。Specific examples of the compound (2) include the formula (1-1), the formula (1-3) to the formula (1-5), the formula (1-7) to the formula (1-9), and the formula (1). 11) a compound represented by the formula (1-16), the formula (1-18) to the formula (1-21), and the formula (1-23) to the formula (1-26), wherein the formula (1) is preferred. 1) A compound represented by the formula (1-3), the formula (1-21), and the formula (1-23) to the formula (1-26). The content of the compound (1) is preferably 1% by mass or more and 99% by mass or less, more preferably 1% by mass or more and 80% by mass or less, and further preferably 3% by mass or more and 70% by mass or less based on the coloring agent (A). the following.

著色劑(A)亦可包含與化合物(1)不同之染料。作為該染料，可列舉油溶性染料、酸性染料、酸性染料之胺鹽或酸性染料之磺醯胺衍生物等染料，例如可列舉於色料索引(The Society of Dyers and Colourists出版)中分至染料一類之化合物、或染色筆記(色染公司)中記載之公知之染料。The colorant (A) may also contain a dye different from the compound (1). Examples of the dye include dyes such as an oil-soluble dye, an acid dye, an amine salt of an acid dye, or a sulfonamide derivative of an acid dye, and are exemplified by a colorant index (published by The Society of Dyers and Colourists). A class of compounds, or known dyes as described in the dyeing notes (color dyeing company).

具體可列舉：C.I.溶劑黃4(以下省略C.I.溶劑黃之記載而僅記載編號)、14、15、23、24、38、62、63、68、82、94、98、99、162；C.I.溶劑紅45、49、125、130；C.I.溶劑橙2、7、11、15、26、56等C.I.溶劑染料；C.I.酸性黃1、3、7、9、11、17、23、25、29、34、36、38、40、42、54、65、72、73、76、79、98、99、111、112、113、114、116、119、123、128、134、135、138、139、140、144、150、155、157、160、161、163、168、169、172、177、178、179、184、190、193、196、197、199、202、203、204、205、207、212、214、220、221、228、230、232、235、238、240、242、243、251；C.I.酸性紅1、4、8、14、17、18、26、27、29、31、34、35、37、42、44、50、51、52、57、66、73、80、87、88、91、92、94、97、103、111、114、129、133、134、138、143、145、150、151、158、176、182、183、198、206、211、215、216、217、227、228、249、252、257、258、260、261、266、268、270、274、277、280、281、195、308、312、315、316、339、341、345、346、349、382、383、394、401、412、417、418、422、426；C.I.酸性橙6、7、8、10、12、26、50、51、52、56、62、63、64、74、75、94、95、107、108、169、173；C.I.酸性紫6B、7、9、17、19等C.I.酸性染料；C.I.直接黃2、33、34、35、38、39、43、47、50、54、58、68、69、70、71、86、93、94、95、98、102、108、109、129、136、138、141；C.I.直接紅79、82、83、84、91、92、96、97、98、99、105、106、107、172、173、176、177、179、181、182、184、204、207、211、213、218、220、221、222、232、233、234、241、243、246、250；C.I.直接橙34、39、41、46、50、52、56、57、61、64、65、68、70、96、97、106、107；C.I.直接紫47、52、54、59、60、65、66、79、80、81、82、84、89、90、93、95、96、103、104等C.I.直接染料；作為C.I.媒染染料，可列舉：C.I.媒染黃5、8、10、16、20、26、30、31、33、42、43、45、56、61、62、65；C.I.媒染紅1、2、3、4、9、11、12、14、17、18、19、22、23、24、25、26、30、32、33、36、37、38、39、41、43、45、46、48、53、56、63、71、74、85、86、88、90、94、95；C.I.媒染橙3、4、5、8、12、13、14、20、21、23、24、28、29、32、34、35、36、37、42、43、47、48；C.I.媒染紫1、2、4、5、7、14、22、24、30、31、32、37、40、41、44、45、47、48、53、58等C.I.媒染染料等。Specific examples thereof include CI Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted, and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; Red 45, 49, 125, 130; CI solvent orange 2, 7, 11, 15, 26, 56 and other CI solvent dyes; CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34 , 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140 , 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 203, 203, 204, 205, 207, 212 , 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145,150,151,158,176,182,183,198,206,211,215,216,217,227,228,249,252,257,258,260,261,266,2 68, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Violet 6B, 7, acidity dyes such as 7, 9, 17, 19; CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94 , 95, 98, 102, 108, 109, 129, 136, 138, 141; CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; CI Direct Orange 34, 39 , 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104 and other CI direct dyes; as CI mordant dyes, can be cited: CI mordant yellow 5, 8, 10, 16, 20, 26 , 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI mordant red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; CI mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI The mordant dyes are 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58 and the like.

著色劑(A)亦可進而包含顏料。作為顏料，可列舉有機顏料，例如C.I.顏料紫1、19、23、29、32、36、38等紫色顏料；C.I.顏料黃1、3、12、13、14、15、16、17、20、24、31、53、83、86、93、94、109、110、117、125、128、137、138、139、147、148、150、153、154、166、173、194、214等黃色顏料；C.I.顏料橙13、31、36、38、40、42、43、51、55、59、61、64、65、71、73等橙色顏料；C.I.顏料紅9、97、105、122、123、144、149、166、168、176、177、180、192、209、215、216、224、242、254、255、264、265等紅色顏料等。其中，較佳為含有選自C.I.顏料黃138、139、150、C.I.顏料紅177、242、254中之至少一種。藉由含有上述顏料，紅色感光性樹脂組合物之透射光譜之最適化容易，耐化學品性變良好。The colorant (A) may further contain a pigment. Examples of the pigment include organic pigments such as violet pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, and 38; CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, Yellow pigments such as 23, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 ; CI pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65,71,73 and other orange pigment; CI pigment red 9, 97, 105, 122, 123, Red pigments such as 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, and the like. Among them, it is preferred to contain at least one selected from the group consisting of C.I. Pigment Yellow 138, 139, 150, C.I. Pigment Red 177, 242, and 254. By containing the above pigment, the transmission spectrum of the red photosensitive resin composition is optimized, and the chemical resistance is improved.

該等顏料可單獨使用或混合使用兩種以上。有機顏料視需要亦可實施松香處理、使用導入有酸性基或鹼性基之顏料衍生物等之表面處理、利用高分子化合物等之對顏料表面之接枝處理、利用硫酸微粒化法等之微粒化處理、或用以去除雜質之利用有機溶劑或水等之清洗處理、利用離子性雜質之離子交換法等的去除處理等。有機顏料較佳為粒徑均勻。藉由含有顏料分散劑進行分散處理，可獲得顏料於溶液中均勻分散之狀態之顏料分散液。These pigments may be used alone or in combination of two or more. The organic pigment may be subjected to a rosin treatment, a surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, a graft treatment on the surface of the pigment by a polymer compound, or the like, or a particle using a sulfuric acid micronization method. The treatment or the removal treatment using an organic solvent or water for removing impurities, the removal treatment by an ion exchange method using ionic impurities, or the like. The organic pigment preferably has a uniform particle size. The pigment dispersion liquid in a state in which the pigment is uniformly dispersed in the solution can be obtained by dispersion treatment with a pigment dispersant.

作為上述顏料分散劑，例如可列舉陽離子系、陰離子系、非離子系、兩性、聚酯系、多胺系、丙烯酸系等之界面活性劑等。該等顏料分散劑可單獨使用亦可組合使用兩種以上。作為顏料分散劑，可列舉商品名KP(信越化學工業(股)製造)、Flowlen(共榮社化學(股)製造)、Solsperse(Zeneca(股)製造)、EFKA(CIBA公司製造)、Ajisper(Ajinomoto Fine-Techno(股)製造)、Disperbyk(BYK Chemie公司製造)等。Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used alone or in combination of two or more. Examples of the pigment dispersant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoei Chemical Co., Ltd.), Solsperse (manufactured by Zeneca), EFKA (manufactured by CIBA), and Ajisper ( Ajinomoto Fine-Techno Co., Ltd., Disperbyk (manufactured by BYK Chemie Co., Ltd.), and the like.

於使用顏料分散劑時，其使用量相對於顏料(A2)較佳為100質量%，更佳為5質量%以上、50質量%以下。若顏料分散劑之使用量在上述範圍內，則有可獲得均勻之分散狀態之顏料分散液之傾向。著色劑(A)中之顏料之含量較佳為1~99質量%，更佳為10~97質量%。When the pigment dispersant is used, the amount thereof is preferably 100% by mass, more preferably 5% by mass or more and 50% by mass or less based on the pigment (A2). When the amount of the pigment dispersant used is within the above range, there is a tendency that a pigment dispersion liquid in a uniformly dispersed state can be obtained. The content of the pigment in the colorant (A) is preferably from 1 to 99% by mass, more preferably from 10 to 97% by mass.

化合物(1)與顏料之含量比率(質量比)較佳為1：99~99：1，更佳為3：97~90：10。藉由設定為此種比率，透射光譜之最適化變容易，良好地獲得高對比度、高亮度。進而，耐熱性、耐化學品性變良好。The content ratio (mass ratio) of the compound (1) to the pigment is preferably from 1:99 to 99:1, more preferably from 3:97 to 90:10. By setting such a ratio, the optimization of the transmission spectrum becomes easy, and high contrast and high luminance are favorably obtained. Further, heat resistance and chemical resistance are improved.

特別是化合物(1)與選自由C.I.顏料黃138、C.I.顏料黃139、C.I.顏料黃150、C.I.顏料紅177、C.I.顏料紅242及C.I.顏料紅254所組成之群中的至少一種之質量比，較佳為3：97~90：10，更佳為3：97~70：30。著色劑(A)之含量相對於著色感光性樹脂組合物中之固體成分較佳為5~60質量%，更佳為8~55質量%，進而佳為10~50質量%。此處，所謂固體成分，係指著色感光性樹脂組合物中將溶劑除外之成分之合計。若著色劑(A)之含量在上述範圍內，則製成彩色濾光片時之色濃度充分，且可於組合物中含有必要量之黏合劑聚合物，故可形成機械強度充分之圖案。In particular, the mass ratio of the compound (1) to at least one selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Red 177, CI Pigment Red 242, and CI Pigment Red 254, It is preferably 3:97 to 90:10, more preferably 3:97 to 70:30. The content of the colorant (A) is preferably from 5 to 60% by mass, more preferably from 8 to 55% by mass, even more preferably from 10 to 50% by mass, based on the solid content of the colored photosensitive resin composition. Here, the solid content refers to the total of the components excluding the solvent in the colored photosensitive resin composition. When the content of the coloring agent (A) is within the above range, the color density of the color filter is sufficient, and a necessary amount of the binder polymer can be contained in the composition, so that a pattern having sufficient mechanical strength can be formed.

本發明之著色感光性樹脂組合物含有樹脂(B)。作為樹脂(B)，並無特別限定，較佳為鹼溶性樹脂。作為樹脂(B)，例如可列舉以下之樹脂[K1]~[K4]等。[K1]具有碳數2~4之環狀醚之單體(a)(以下有時稱為「(a)」)、與選自由不飽和羧酸及不飽和羧酸酐所組成之群中的至少一種(b)(以下有時稱為「(b)」)之共聚物。[K2](a)、(b)及可與(a)共聚合之單體(c)(此處與(a)及(b)不同)(以下有時稱為「(c)」)之共聚物[K3](b)與(c)之共聚物[K4]使(a)與(b)和(c)之共聚物反應所得之樹脂。The colored photosensitive resin composition of the present invention contains a resin (B). The resin (B) is not particularly limited, and is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K4]. [K1] a monomer (a) having a cyclic ether having 2 to 4 carbon atoms (hereinafter sometimes referred to as "(a)"), and a group selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides At least one (b) (hereinafter sometimes referred to as "(b)") copolymer. [K2] (a), (b) and a monomer (c) which can be copolymerized with (a) (here different from (a) and (b)) (hereinafter sometimes referred to as "(c)") Copolymer [K3] (b) and (c) copolymer [K4] A resin obtained by reacting (a) with a copolymer of (b) and (c).

藉由使樹脂(B)含有來源於(a)之結構單元，可進一步提高所得著色圖案之耐熱性、耐化學品性等可靠性。By including the structural unit derived from (a) in the resin (B), the reliability of heat resistance and chemical resistance of the obtained colored pattern can be further improved.

(a)例如係指具有碳數2~4之環狀醚(例如選自由環氧乙烷環、氧雜環丁烷環及四氫呋喃環(氧雜環戊烷環)所組成之群中之至少一種)與環狀醚以外之聚合性基之聚合性化合物。(a)較佳為具有碳數2~4之環狀醚與乙烯性碳-碳雙鍵之單體，更佳為具有碳數2~4之環狀醚與(甲基)丙烯醯氧基之單體。(a) means, for example, a cyclic ether having a carbon number of 2 to 4 (for example, selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring)) A polymerizable compound which is a polymerizable group other than a cyclic ether. (a) preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and an ethylenic carbon-carbon double bond, more preferably a cyclic ether having a carbon number of 2 to 4 and a (meth)acryloxy group. Monomer.

又，本說明書中，所謂「(甲基)丙烯酸」，表示選自由丙烯酸及甲基丙烯酸所組成之群中之至少一種。「(甲基)丙烯醯基」及「(甲基)丙烯酸酯」等表述亦具有相同之含意。In the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth)acryloyl" and "(meth)acrylate" have the same meaning.

作為(a)，例如可列舉具有環氧乙烷基之單體(a1)(以下有時稱為「(a1)」)、具有氧雜環丁烷基之單體(a2)(以下有時稱為「(a2)」)、具有四氫呋喃基之單體(a3)(以下有時稱為「(a3)」)等。其中，較佳為具有環氧乙烷基之單體(a1)，更佳為具有將環式烯烴加以環氧化而成之結構之單體(a1-2)(以下有時稱為「(a1-2)」)。所謂具有環氧乙烷基之單體(a1)，係指具有環氧乙烷基與環氧乙烷基以外之聚合性基之聚合性化合物。(a1)例如可列舉具有將鏈式烯烴加以環氧化而成之結構之單體(a1-1)(以下有時稱為「(a1-1)」)、具有將環式烯烴加以環氧化而成之結構之單體(a1-2)。(a), for example, a monomer (a1) having an oxiranyl group (hereinafter sometimes referred to as "(a1)") or a monomer (a2) having an oxetanyl group (hereinafter sometimes referred to) The monomer (a3) having a tetrahydrofuran group (hereinafter sometimes referred to as "(a3)") or the like is referred to as "(a2)"). Among them, a monomer (a1) having an oxiranyl group is preferred, and a monomer (a1-2) having a structure in which a cyclic olefin is epoxidized is more preferred (hereinafter sometimes referred to as "(a1) -2)"). The monomer (a1) having an oxiranyl group means a polymerizable compound having a polymerizable group other than an oxirane group and an oxirane group. (a1), for example, a monomer (a1-1) having a structure in which a chain olefin is epoxidized (hereinafter sometimes referred to as "(a1-1)")), and having a cyclic olefin epoxidized The monomer of the structure (a1-2).

作為(a1)，較佳為具有環氧乙烷基與乙烯性碳-碳雙鍵之單體，更佳為具有環氧乙烷基與(甲基)丙烯醯氧基之單體。As (a1), a monomer having an oxirane group and an ethylenic carbon-carbon double bond is preferred, and a monomer having an oxirane group and a (meth) propylene decyloxy group is more preferred.

作為(a1-1)，可列舉(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸-β-甲基縮水甘油酯、(甲基)丙烯酸-β-乙基縮水甘油酯、縮水甘油基乙烯醚、鄰乙烯基苄基縮水甘油醚、間乙烯基苄基縮水甘油醚、對乙烯基苄基縮水甘油醚、α-甲基-鄰乙烯基苄基縮水甘油醚、α-甲基-間乙烯基苄基縮水甘油醚、α-甲基-對乙烯基苄基縮水甘油醚、2,3-雙(縮水甘油氧基甲基)苯乙烯、2,4-雙(縮水甘油氧基甲基)苯乙烯、2,5-雙(縮水甘油氧基甲基)苯乙烯、2,6-雙(縮水甘油氧基甲基)苯乙烯、2,3,4-三(縮水甘油氧基甲基)苯乙烯、2,3,5-三(縮水甘油氧基甲基)苯乙烯、2,3,6-三(縮水甘油氧基甲基)苯乙烯、3,4,5-三(縮水甘油氧基甲基)苯乙烯、2,4,6-三(縮水甘油氧基甲基)苯乙烯等。作為(a1-2)，可列舉一氧化乙烯基環己烯、1,2-環氧-4-乙烯基環己烷(例如Celloxide 2000，大賽璐化學工業(股)製造)、(甲基)丙烯酸-3,4-環氧環己基甲酯(例如Cyclomer A400，大賽璐化學工業(股)製造)、(甲基)丙烯酸-3,4-環氧環己基甲酯(例如Cyclomer M100，大賽璐化學工業(股)製造)、式(I)所示化合物及式(II)所示化合物等。Examples of (a1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and glycidylethylene. Ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-inter-ethylene Glycidyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidoxymethyl)styrene, 2,4-bis(glycidoxymethyl) Styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris(glycidoxymethyl) Styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris (glycidyloxy) Methyl)styrene, 2,4,6-tris(glycidoxymethyl)styrene, and the like. Examples of (a1-2) include monooxyethylene cyclohexene and 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000, manufactured by Daicel Chemical Industries Co., Ltd.), (methyl). 3,4-epoxycyclohexyl methyl acrylate (eg Cyclomer A400, manufactured by Daicel Chemical Industries, Inc.), 3,4-epoxycyclohexyl methyl (meth)acrylate (eg Cyclomer M100, Daicel) A chemical industry (manufactured by the Chemical Industry Co., Ltd.), a compound represented by the formula (I), a compound represented by the formula (II), and the like.

[式(I)及式(II)中，Ra 及Rb 彼此獨立表示氫原子或碳數1~4之烷基，該烷基所含之氫原子可經羥基取代。X1 及X2 彼此獨立表示單鍵、-Rc -、＊-Rc -O-、＊-Rc -S-、＊-Rc -NH-。Rc 表示碳數1~6之烷二基。In the formulae (I) and (II), R a and R b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. X 1 and X 2 independently represents a single bond, -R c each other -, * - R c -O - , * - R c -S -, * - R c -NH-. R c represents an alkanediyl group having 1 to 6 carbon atoms.

＊表示與O之結合鍵]作為碳數1~4之烷基，可列舉甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基等。作為氫原子經羥基取代之烷基，可列舉羥基甲基、1-羥基乙基、2-羥基乙基、1-羥基丙基、2-羥基丙基、3-羥基丙基、1-羥基-1-甲基乙基、2-羥基-1-甲基乙基、1-羥基丁基、2-羥基丁基、3-羥基丁基、4-羥基丁基等。作為Ra 及Rb ，較佳可列舉氫原子、甲基、羥基甲基、1-羥基乙基、2-羥基乙基，更佳可列舉氫原子、甲基。作為烷二基，可列舉亞甲基、伸乙基、丙烷-1,2-二基、丙烷-1,3-二基、丁烷-1,4-二基、戊烷-1,5-二基、己烷-1,6-二基等。* indicates a bond to O.] The alkyl group having 1 to 4 carbon atoms may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group or a t-butyl group. Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and a 1-hydroxy group. 1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like. R a and R b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group. Examples of the alkanediyl group include a methylene group, an ethylidene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5- group. Dibasic, hexane-1,6-diyl and the like.

作為X1 及X2 ，較佳可列舉單鍵、亞甲基、伸乙基、＊-CH2 -O-(＊表示與O之結合鍵)基、＊-CH2 CH2 -O-基，更佳可列舉單鍵、＊-CH2 CH2 -O-基。作為式(I)所示化合物，可列舉式(I-1)~式(I-15)所示化合物等。較佳可列舉式(I-1)、式(I-3)、式(I-5)、式(I-7)、式(I-9)、式(I-11)~式(I-15)。更佳可列舉式(I-1)、式(I-7)、式(I-9)、式(I-15)。As X 1 and X 2 , a single bond, a methylene group, an ethylidene group, a *-CH 2 -O- (* represents a bond with O) group, and a *-CH 2 CH 2 -O- group are preferable. More preferably, it is a single bond, *-CH 2 CH 2 -O- group. The compound represented by the formula (I) may, for example, be a compound represented by the formula (I-1) to the formula (I-15). Preferably, the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9), the formula (I-11) to the formula (I- 15). More preferably, the formula (I-1), the formula (I-7), the formula (I-9), and the formula (I-15) can be enumerated.

作為式(II)所示化合物，可列舉式(II-1)~式(II-15)所示化合物等。較佳可列舉式(II-1)、式(II-3)、式(II-5)、式(II-7)、式(II-9)、式(II-11)~式(II-15)。更佳可列舉式(II-1)、式(II-7)、式(II-9)、式(II-15)。The compound represented by the formula (II) includes a compound represented by the formula (II-1) to the formula (II-15). Preferably, the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II-9), the formula (II-11) to the formula (II- 15). More preferably, it is a formula (II-1), Formula (II-7), Formula (II-9), Formula (II-15).

式(I)所示化合物及式(II)所示化合物可分別單獨使用。又，亦可將該等以任意比率混合。混合時，其混合比率以莫耳比計較佳為式(I)：式(II)為5：95~95：5，更佳為10：90~90：10，特佳為20：80~80：20。The compound of the formula (I) and the compound of the formula (II) can be used alone. Further, these may be mixed at any ratio. When mixing, the mixing ratio is preferably Formula (I) in terms of molar ratio: Formula (II) is 5:95 to 95:5, more preferably 10:90 to 90:10, and particularly preferably 20:80 to 80. :20.

所謂具有氧雜環丁烷基之單體(a2)，係指具有氧雜環丁烷基與氧雜環丁烷基以外之聚合性基之聚合性化合物。作為(a2)，較佳為具有氧雜環丁烷基與乙烯性碳-碳雙鍵之單體，更佳為具有氧雜環丁烷基與(甲基)丙烯醯氧基之單體。作為(a2)，可列舉3-甲基-3-甲基丙烯醯氧基甲基氧雜環丁烷、3-甲基-3-丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-甲基丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-丙烯醯氧基甲基氧雜環丁烷、3-甲基-3-甲基丙烯醯氧基乙基氧雜環丁烷、3-甲基-3-丙烯醯氧基乙基氧雜環丁烷、3-乙基-3-甲基丙烯醯氧基乙基氧雜環丁烷、3-乙基-3-丙烯醯氧基乙基氧雜環丁烷等。The monomer (a2) having an oxetane group means a polymerizable compound having a polymerizable group other than an oxetane group and an oxetanyl group. As (a2), a monomer having an oxetane group and an ethylenic carbon-carbon double bond is preferred, and a monomer having an oxetane group and a (meth) propylene decyloxy group is more preferred. Examples of (a2) include 3-methyl-3-methylpropenyloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, and 3-ethyl b. 3-methylpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-methylpropenyloxy Ethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methylpropenyloxyethyloxetane, 3- Ethyl-3-propenyloxyethyloxetane and the like.

所謂具有四氫呋喃基之單體(a3)，係指具有四氫呋喃基與四氫呋喃基以外之聚合性基之聚合性化合物。作為(a3)，較佳為具有四氫呋喃基與乙烯性碳-碳雙鍵之單體，更佳為具有四氫呋喃基與(甲基)丙烯醯氧基之單體。作為(a3)，具體可列舉丙烯酸四氫糠酯(例如Viscoat V＃150，大阪有機化學工業(股)製造)、甲基丙烯酸四氫糠酯等。The monomer (a3) having a tetrahydrofuran group means a polymerizable compound having a polymerizable group other than a tetrahydrofuranyl group and a tetrahydrofuranyl group. As (a3), a monomer having a tetrahydrofuranyl group and an ethylenic carbon-carbon double bond is preferred, and a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group is more preferred. Specific examples of (a3) include tetrahydrofurfuryl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

作為(a)，就可進一步提高所得著色圖案之耐熱性、耐化學品性等可靠性之方面而言，較佳為(a1)。進而，就著色感光性樹脂組合物之保存穩定性優異之觀點而言，更佳為(a1-2)。(a) is preferably (a1) in terms of further improving the reliability of heat resistance and chemical resistance of the obtained colored pattern. Further, from the viewpoint of excellent storage stability of the colored photosensitive resin composition, (a1-2) is more preferable.

作為(b)，具體而言，例如可列舉：丙烯酸、甲基丙烯酸、丁烯酸、鄰/間/對乙烯基苯甲酸等不飽和單羧酸類；順丁烯二酸、反丁烯二酸、甲基順丁烯二酸、甲基反丁烯二酸、衣康酸、3-乙烯基鄰苯二甲酸、4-乙烯基鄰苯二甲酸、3,4,5,6-四氫鄰苯二甲酸、1,2,3,6-四氫鄰苯二甲酸、二甲基四氫鄰苯二甲酸、1,4-環己烯二羧酸等不飽和二羧酸類；甲基-5-降烯-2,3-二羧酸、5-羧基雙環[2.2.1]庚-2-烯、5,6-二羧基雙環[2.2.1]庚-2-烯、5-羧基-5-甲基雙環[2.2.1]庚-2-烯、5-羧基-5-乙基雙環[2.2.1]庚-2-烯、5-羧基-6-甲基雙環[2.2.1]庚-2-烯、5-羧基-6-乙基雙環[2.2.1]庚-2-烯等含有羧基之雙環不飽和化合物類；順丁烯二酸酐、甲基順丁烯二酸酐、衣康酸酐、3-乙烯基鄰苯二甲酸酐、4-乙烯基鄰苯二甲酸酐、3,4,5,6-四氫鄰苯二甲酸酐、1,2,3,6-四氫鄰苯二甲酸酐、二甲基四氫鄰苯二甲酸酐、5,6-二羧基雙環[2.2.1]庚-2-烯酐(雙環庚烯二甲酸酐)等不飽和二羧酸類酐；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]酯等二元以上之多元羧酸之不飽和單[(甲基)丙烯醯氧基烷基]酯類；α-(羥基甲基)丙烯酸之類的於同一分子中含有羥基及羧基之不飽和丙烯酸酯類等。Specific examples of (b) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-/m-/p-vinylbenzoic acid, and maleic acid and fumaric acid. , methyl maleic acid, methyl fumaric acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydroortene Unsaturated dicarboxylic acid such as phthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid or 1,4-cyclohexene dicarboxylic acid; methyl-5 -drop Alkene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-A Bicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2 - a bicyclic unsaturated compound containing a carboxyl group such as a olefin or a 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, methyl maleic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic acid An unsaturated dicarboxylic acid anhydride such as an acid anhydride, dimethyltetrahydrophthalic anhydride or 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (bicycloheptene dicarboxylic anhydride); [2-(Methyl) propylene oxiranyl ethyl] ester, phthalic acid mono [2-(methyl) propylene oxyethyl] ester, etc. Methyl)acryloxyalkylene esters; unsaturated acrylates having a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid.

該等中，就共聚合反應性之觀點或於鹼水溶液中之溶解性之觀點而言，較佳為丙烯酸、甲基丙烯酸、順丁烯二酸酐等。Among these, from the viewpoint of the copolymerization reactivity or the solubility in an aqueous alkali solution, acrylic acid, methacrylic acid, maleic anhydride or the like is preferable.

作為(c)，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸-2-甲基環己酯、(甲基)丙烯酸三環[5.2.1.02,6 ]癸烷-8-基酯(該技術領域中，慣用名為(甲基)丙烯酸二環戊酯)、(甲基)丙烯酸二環戊氧基乙酯、(甲基)丙烯酸異酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸炔丙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸苄酯等(甲基)丙烯酸酯類；(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯等含羥基之(甲基)丙烯酸酯類；順丁烯二酸二乙酯、反丁烯二酸二乙酯、衣康酸二乙酯等二羧酸二酯；雙環[2.2.1]庚-2-烯、5-甲基雙環[2.2.1]庚-2-烯、5-乙基雙環[2.2.1]庚-2-烯、5-羥基雙環[2.2.1]庚-2-烯、5-羥基甲基雙環[2.2.1]庚-2-烯、5-(2'-羥基乙基)雙環[2.2.1]庚-2-烯、5-甲氧基雙環[2.2.1]庚-2-烯、5-乙氧基雙環[2.2.1]庚-2-烯、5,6-二羥基雙環[2.2.1]庚-2-烯、5,6-二(羥基甲基)雙環[2.2.1]庚-2-烯、5,6-二(2'-羥基乙基)雙環[2.2.1]庚-2-烯、5,6-二甲氧基雙環[2.2.1]庚-2-烯、5,6-二乙氧基雙環[2.2.1]庚-2-烯、5-羥基-5-甲基雙環[2.2.1]庚-2-烯、5-羥基-5-乙基雙環[2.2.1]庚-2-烯、5-羥基甲基-5-甲基雙環[2.2.1]庚-2-烯、5-第三丁氧基羰基雙環[2.2.1]庚-2-烯、5-環己氧基羰基雙環[2.2.1]庚-2-烯、5-苯氧基羰基雙環[2.2.1]庚-2-烯、5,6-雙(第三丁氧基羰基)雙環[2.2.1]庚-2-烯、5,6-雙(環己氧基羰基)雙環[2.2.1]庚-2-烯等雙環不飽和化合物類；N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苄基順丁烯二醯亞胺、N-琥珀醯亞胺基-3-順丁烯二醯亞胺苯甲酸酯、N-琥珀醯亞胺基-4-順丁烯二醯亞胺丁酸酯、N-琥珀醯亞胺基-6-順丁烯二醯亞胺己酸酯、N-琥珀醯亞胺基-3-順丁烯二醯亞胺丙酸酯、N-(9-吖啶基)順丁烯二醯亞胺等二羰基醯亞胺衍生物類；苯乙烯、α-甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、乙烯基甲苯、對甲氧基苯乙烯、丙烯腈、甲基丙烯腈、氯乙烯、偏二氯乙烯、丙烯醯胺、甲基丙烯醯胺、乙酸乙烯酯、1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯等。Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and (meth)acrylic acid. Tributyl ester, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid Cyclopentyl ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 ]decane-8-yl (meth)acrylate In the technical field, it is commonly used as dicyclopentyl (meth)acrylate), dicyclopentyloxyethyl (meth)acrylate, and (meth)acrylic acid. Ester, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, (meth)acrylic acid a (meth) acrylate such as benzyl ester; a hydroxyl group-containing (meth) acrylate such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; a dicarboxylic acid diester such as diethyl acid diethyl ester, diethyl fumarate or diethyl itaconate; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]g 2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2 - alkene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2 .1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5 ,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethyl Oxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]heptane- 2-ene, 5-hydroxymethyl-5-A Bicyclo[2.2.1]hept-2-ene, 5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis ( a bicyclic unsaturated compound such as cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenyl maleimide, N-cyclohexylmethyleneimine, N- Benzyl succinimide, N-succinimide-3-butyleneimine benzoate, N-succinimide-4-butyleneimine Acid ester, N-succinimide-6-m-butyleneimine hexanoate, N-succinimide-3-oxenimide propionate, N-(9- Acridine-based dicarbonyl ruthenium derivatives such as maleimide; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxy Styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3 - dimethyl-1,3-butadiene or the like.

該等中，就共聚合反應性及耐熱性之方面而言，較佳為苯乙烯、N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苄基順丁烯二醯亞胺、雙環[2.2.1]庚-2-烯等。樹脂[K1]中，來源於各單體之結構單元之比率較佳為於構成樹脂[K1]之所有結構單元中在以下範圍內。來源於(a)之結構單元：60~98莫耳%(更佳為65~95莫耳%)來源於(b)之結構單元；2~40莫耳%(更佳為5~35莫耳%)若樹脂[K1]之結構單元之比率在上述範圍內，則有保存穩定性、顯影性、硬化圖案之耐溶劑性變良好之傾向。樹脂[K1]例如可參考文獻「高分子合成之實驗法」(大津隆行著，化學同人(股)出版社，第1版第1印次，1972年3月1日發行)中記載之方法及該文獻中記載之引用文獻而製造。Among these, in terms of copolymerization reactivity and heat resistance, styrene, N-phenyl maleimide, N-cyclohexylmethyleneimine, N-benzyl are preferred. A cis-butenylene imine, a bicyclo [2.2.1] hept-2-ene, and the like. In the resin [K1], the ratio of the structural unit derived from each monomer is preferably within the following range among all the structural units constituting the resin [K1]. The structural unit derived from (a): 60 to 98 mol% (more preferably 65 to 95 mol%) derived from the structural unit of (b); 2 to 40 mol% (more preferably 5 to 35 mol) %) When the ratio of the structural unit of the resin [K1] is within the above range, storage stability, developability, and solvent resistance of the cured pattern tend to be improved. The resin [K1] can be referred to, for example, the method described in the "Experimental Method for Polymer Synthesis" (Dazu Takashi, Chemical Tongren (Stock) Press, 1st Edition, 1st Print, issued on March 1, 1972) and It is manufactured by reference to the documents described in the literature.

具體可例示以下方法：將預定量之(a)及(b)、聚合起始劑及溶劑等加入至反應容器中，利用氮氣置換氧氣，藉此於脫氧環境下進行攪拌、加熱、保溫。再者，此處所用之聚合起始劑及溶劑等並無特別限定，可任意使用該領域中通常所使用者。例如，作為聚合起始劑，可列舉偶氮化合物(2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2,4-二甲基戊腈)等)或有機過氧化物(過氧化苯甲醯等)，作為溶劑，只要係溶解各單體者即可，可使用下文中作為感光性樹脂組合物之溶劑而描述之溶劑等。Specifically, a method may be exemplified in which a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are added to a reaction vessel, and oxygen is replaced with nitrogen gas to carry out stirring, heating, and heat preservation in a deoxidizing atmosphere. In addition, the polymerization initiator, solvent, and the like used herein are not particularly limited, and any user in the field can be arbitrarily used. For example, examples of the polymerization initiator include an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic The oxide (such as benzamidine peroxide) may be used as a solvent, and a solvent or the like described below as a solvent of the photosensitive resin composition may be used.

再者，所得之共聚物可直接使用反應後之溶液，亦可使用經濃縮或稀釋之溶液，亦可使用藉由再沈澱等方法以固體(粉體)形式取出者。特別是藉由在該聚合時使用後述之溶劑(D)作為溶劑，可直接使用反應後之溶液，從而可使製造步驟簡化。Further, the obtained copolymer may be directly used as a solution after the reaction, or a solution which is concentrated or diluted, or may be used as a solid (powder) by reprecipitation or the like. In particular, by using the solvent (D) described later as a solvent in the polymerization, the solution after the reaction can be used as it is, and the production steps can be simplified.

樹脂[K2]中，較佳為來源於各單體之結構單元之比率於構成樹脂[K2]之所有結構單元中在以下範圍內。In the resin [K2], it is preferred that the ratio of the structural unit derived from each monomer is within the following range among all the structural units constituting the resin [K2].

來源於(a)之結構單元：2~95莫耳%(更佳為5~80莫耳%)The structural unit derived from (a): 2 to 95 mol% (more preferably 5 to 80 mol%)

來源於(b)之結構單元：2~40莫耳%(更佳為5~35莫耳%)The structural unit derived from (b): 2 to 40 mol% (more preferably 5 to 35 mol%)

來源於(c)之結構單元：1~65莫耳%(更佳為1~60莫耳%)The structural unit derived from (c): 1 to 65 mol% (more preferably 1 to 60 mol%)

若樹脂[K2]之結構單元之比率在上述範圍內，則有保存穩定性、顯影性、硬化圖案之耐溶劑性、耐熱性及機械強度變良好之傾向。When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability, the developability, the solvent resistance of the cured pattern, the heat resistance, and the mechanical strength tend to be improved.

樹脂[K2]例如可與作為樹脂[K1]之製造方法而記載之方法同樣地製造。The resin [K2] can be produced, for example, in the same manner as the method described in the production method of the resin [K1].

具體可列舉以下方法：將預定量之(a)、(b)及(c)、聚合起始劑及溶劑加入至反應容器中，藉由氮氣置換氧氣，藉此於脫氧環境下進行攪拌、加熱、保溫。所得之共聚物可直接使用反應後之溶液，亦可使用經濃縮或稀釋之溶液，亦可使用藉由再沈澱等方法以固體(粉體)形式取出者。Specifically, a method of adding a predetermined amount of (a), (b), and (c), a polymerization initiator, and a solvent to a reaction vessel, and replacing the oxygen with nitrogen, thereby stirring and heating in a deoxidizing atmosphere Insulation. The obtained copolymer may be directly used as a solution after the reaction, or a solution which is concentrated or diluted, or may be used as a solid (powder) by reprecipitation or the like.

樹脂[K3]中，較佳為來源於各單體之結構單元之比率於構成樹脂[K3]之所有結構單元中在以下範圍內。In the resin [K3], it is preferred that the ratio of the structural unit derived from each monomer is within the following range among all the structural units constituting the resin [K3].

(b)2~40莫耳%，更佳為5~35莫耳%(b) 2 to 40 mol%, more preferably 5 to 35 mol%

(c)60~98莫耳%，更佳為65~95莫耳%(c) 60 to 98% by mole, more preferably 65 to 95% by mole

樹脂[K3]例如可與作為樹脂[K1]之製造方法而記載之方法同樣地製造。The resin [K3] can be produced, for example, in the same manner as the method described in the production method of the resin [K1].

樹脂[K4]可藉由獲得(b)與(c)之共聚物，並對(a)所具有之碳數2~4之環狀醚加成(c)所具有之羧基而獲得。The resin [K4] can be obtained by obtaining a copolymer of (b) and (c) and adding (a) a carboxyl group having 2 to 4 carbon atoms which is contained in (a).

首先，與作為[K1]之製造方法而記或之方法同樣地製造(b)與(c)之共聚物。此時，較佳為來源於各單體之結構單元之比率於構成(b)與(c)之共聚物之所有結構單元中在以下範圍內。First, a copolymer of (b) and (c) is produced in the same manner as the method described in [K1]. In this case, it is preferred that the ratio of the structural unit derived from each monomer is within the following range among all the structural units constituting the copolymer of (b) and (c).

(b)5~50莫耳%，更佳為10~45莫耳%(b) 5 to 50 mol%, more preferably 10 to 45 mol%

(c)50~95莫耳%，更佳為55~90莫耳%(c) 50 to 95% by mole, more preferably 55 to 90% by mole

繼而，使(a)所具有之碳數2~4之環狀醚與上述共聚物中來源於(c)之結構單元所含之羧基及/或羧酸酐的一部分反應。Then, the cyclic ether having 2 to 4 carbon atoms which is contained in (a) is reacted with a part of the carboxyl group and/or the carboxylic anhydride contained in the structural unit derived from (c) in the copolymer.

繼(b)與(c)之共聚物之製造後，將燒瓶內環境由氮氣置換成空氣，將(a)、相對於(a)~(c)之合計量而通常為0.001~5質量%之羧基與環狀醚之反應觸媒(例如三(二甲基胺基甲基)苯酚等)、及相對於(a)~(c)之合計量而通常為0.001~5質量%之聚合抑制劑(例如對苯二酚等)等加入至燒瓶內，通常於60~130℃下反應1~10小時，藉此可獲得樹脂[K4]。添加方法、反應溫度及時間等反應條件可考慮製造設備或聚合之發熱量等而適當調整。再者，與聚合條件相同，可考慮製造設備或聚合之發熱量等而適當調整添加方法或反應溫度。After the production of the copolymer of (b) and (c), the atmosphere in the flask is replaced with air by nitrogen, and (a) is usually 0.001 to 5% by mass relative to the total of (a) to (c). The polymerization reaction of the carboxyl group and the cyclic ether (for example, tris(dimethylaminomethyl)phenol), and the polymerization inhibition of 0.001 to 5% by mass based on the total amount of (a) to (c) A reagent (for example, hydroquinone or the like) or the like is added to the flask, and is usually reacted at 60 to 130 ° C for 1 to 10 hours, whereby a resin [K4] can be obtained. The reaction conditions such as the addition method, the reaction temperature, and the time can be appropriately adjusted in consideration of the heat generation amount of the production equipment or the polymerization. Further, in the same manner as the polymerization conditions, the addition method or the reaction temperature can be appropriately adjusted in consideration of the production equipment or the calorific value of the polymerization.

此時之(a)之使用量相對於(b)而較佳為5~80莫耳%，更佳為10~75莫耳%，進而佳為15~70莫耳%。藉由設定為該範圍，有保存穩定性、顯影性、耐溶劑性、耐熱性、機械強度及感度之平衡變良好之傾向。The amount of use of (a) at this time is preferably 5 to 80 mol%, more preferably 10 to 75 mol%, and even more preferably 15 to 70 mol%, relative to (b). By setting it as this range, the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity tends to become favorable.

作為樹脂(B)，具體可列舉：(甲基)丙烯酸-3,4-環氧環己基甲酯/(甲基)丙烯酸共聚物、丙烯酸-3,4-環氧三環[5.2.1.02.6 ]癸基酯/(甲基)丙烯酸共聚物等樹脂[K1]；(甲基)丙烯酸縮水甘油酯/(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸縮水甘油酯/苯乙烯/(甲基)丙烯酸共聚物、丙烯酸-3,4-環氧三環[5.2.1.02.6 ]癸基酯/(甲基)丙烯酸/N-環己基順丁烯二醯亞胺共聚物、3-甲基-3-(甲基)丙烯醯氧基甲基氧雜環丁烷/(甲基)丙烯酸/苯乙烯共聚物等樹脂[K2]；(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、苯乙烯/(甲基)丙烯酸共聚物等樹脂[K3]；對(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物加成(甲基)丙烯酸縮水甘油酯所得之樹脂、對(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙烯酸共聚物加成(甲基)丙烯酸縮水甘油酯所得之樹脂、對(甲基)丙烯酸三環癸酯/(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物加成(甲基)丙烯酸縮水甘油酯所得之樹脂等樹脂[K4]等。其中，較佳為樹脂[K1]及樹脂[K2]，更佳為樹脂[K1]，進而佳為丙烯酸-3,4-環氧三環[5.2.1.02.6 ]癸基酯/(甲基)丙烯酸共聚物。Specific examples of the resin (B) include (meth)acrylic acid-3,4-epoxycyclohexylmethyl ester/(meth)acrylic acid copolymer, and acrylic-3,4-epoxytricyclo[5.2.1.0 2.6 Resin such as mercaptoester/(meth)acrylic copolymer [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidol (meth)acrylate Ester/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricycloacrylate [5.2.1.0 2.6 ]decyl ester/(meth)acrylic acid/N-cyclohexylmethyleneimine Copolymer, 3-methyl-3-(meth)acryloxymethyloxybutane/(meth)acrylic acid/styrene copolymer, etc. [K2]; benzyl (meth)acrylate/ (Meth)acrylic acid copolymer, resin such as styrene/(meth)acrylic acid copolymer [K3]; addition of benzyl (meth)acrylate/(meth)acrylic acid copolymer to glycidyl (meth)acrylate The obtained resin, a resin obtained by adding a tricyclodecyl (meth) acrylate/styrene/(meth)acrylic acid copolymer to a glycidyl (meth)acrylate, and a tricyclodecyl (meth)acrylate/ Benzyl (meth)acrylate/(meth)acrylic acid copolymerization Addition (meth) acrylate ester resin obtained from resin [K4] and the like. Wherein, preferably the resin [Kl] and the resin [K2], more preferably a resin [Kl], 3,4-epoxy acrylate is further excellent tricyclo [5.2.1.0 2.6] decyl acrylate / (meth) Acrylic copolymer.

樹脂(B)之聚苯乙烯換算之重量平均分子量較佳為3,000~100,000，更佳為5,000~50,000，進而佳為5,000~35,000，進而更佳為6,000~30,000，特佳為7,000~28,000。若分子量在上述範圍內，則有塗膜硬度提昇、殘膜率亦較高、未曝光部對顯影液之溶解性良好、解析度提高之傾向。The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, further preferably from 5,000 to 35,000, more preferably from 6,000 to 30,000, and particularly preferably from 7,000 to 28,000. When the molecular weight is within the above range, the hardness of the coating film is increased, the residual film ratio is also high, the solubility of the unexposed portion to the developer is good, and the resolution tends to be improved.

樹脂(B)之分子量分佈[重量平均分子量(Mw)/數量平均分子量(Mn)]較佳為1.1~6，更佳為1.2~4。The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably from 1.1 to 6, more preferably from 1.2 to 4.

樹脂(B)之酸值較佳為50~150，更佳為60~135，進而佳為70~135。此處，酸值係作為將樹脂(B)1 g中和所必需之氫氧化鉀之量(mg)而測定之值，例如可藉由使用氫氧化鉀水溶液進行滴定而求出。The acid value of the resin (B) is preferably from 50 to 150, more preferably from 60 to 135, and still more preferably from 70 to 135. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

樹脂(B)之含量相對於著色感光性樹脂組合物之固體成分較佳為7~65質量%，更佳為13~60質量%，進而佳為17~55質量%。若樹脂(B)之含量在上述範圍內，則可形成圖案，且有解析度及殘膜率提高之傾向。The content of the resin (B) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, even more preferably from 17 to 55% by mass, based on the solid content of the colored photosensitive resin composition. When the content of the resin (B) is within the above range, a pattern can be formed, and the resolution and the residual film ratio tend to be improved.

本發明之著色感光性樹脂組合物含有光聚合性化合物(C)。光聚合性化合物(C)只要係可利用藉由照射光而由光聚合起始劑(D)產生之活性自由基、酸等進行聚合之化合物，則並無特別限定。例如可列舉具有聚合性之碳-碳不飽和鍵之化合物等。The colored photosensitive resin composition of the present invention contains a photopolymerizable compound (C). The photopolymerizable compound (C) is not particularly limited as long as it can be polymerized by an active radical, an acid or the like generated by a photopolymerization initiator (D) by irradiation with light. For example, a compound having a polymerizable carbon-carbon unsaturated bond or the like can be given.

作為上述光聚合性化合物(C)，較佳為3官能以上之多官能之光聚合性化合物。作為3官能以上之多官能之光聚合性化合物，例如可列舉季戊四醇四丙烯酸酯、季戊四醇四甲基丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇五甲基丙烯酸酯、二季戊四醇六丙烯酸酯、二季戊四醇六甲基丙烯酸酯等。上述光聚合性化合物(C)可單獨使用亦可組合使用兩種以上。The photopolymerizable compound (C) is preferably a trifunctional or higher polyfunctional photopolymerizable compound. Examples of the trifunctional or higher polyfunctional photopolymerizable compound include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol. Hexamethyl acrylate and the like. The photopolymerizable compound (C) may be used alone or in combination of two or more.

光聚合性化合物(C)之含量相對於著色感光性樹脂組合物之固體成分較佳為7~65質量%，更佳為13~60質量%，進而佳為17~55質量%。若上述光聚合性化合物(C)之含量在上述範圍內，則有硬化充分進行而顯影前後之膜厚比率提高，且圖案中不易出現底切而密接性變良好之傾向，故較佳。The content of the photopolymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, even more preferably from 17 to 55% by mass, based on the solid content of the colored photosensitive resin composition. When the content of the photopolymerizable compound (C) is within the above range, the curing is sufficiently performed, and the film thickness ratio before and after the development is improved, and the undercut is less likely to occur in the pattern, and the adhesion tends to be good, which is preferable.

本發明之著色感光性樹脂組合物含有光聚合起始劑(D)。The colored photosensitive resin composition of the present invention contains a photopolymerization initiator (D).

作為上述光聚合起始劑(D)，只要係藉由光之作用而產生活性自由基、酸等引發聚合之化合物，則並無特別限定，可使用公知之聚合起始劑。光聚合起始劑(D)亦可於含有藉由光之作用而產生活性自由基、酸等之化合物之同時含有光聚合起始助劑(D1)。光聚合起始助劑(D1)係用於促進由光聚合起始劑引發聚合之光聚合性化合物之聚合的化合物、或增感劑。The photopolymerization initiator (D) is not particularly limited as long as it generates a compound which initiates polymerization such as an active radical or an acid by the action of light, and a known polymerization initiator can be used. The photopolymerization initiator (D) may also contain a photopolymerization initiation aid (D1) while containing a compound which generates an active radical, an acid or the like by the action of light. The photopolymerization initiation aid (D1) is a compound or a sensitizer for promoting polymerization of a photopolymerizable compound which initiates polymerization by a photopolymerization initiator.

作為光聚合起始劑(D)，較佳為藉由光之作用而產生活性自由基之化合物，更佳為苯乙酮化合物、三化合物、醯基氧化膦化合物、肟化合物及聯咪唑化合物。As the photopolymerization initiator (D), a compound which generates an active radical by the action of light is preferred, and an acetophenone compound, preferably A compound, a mercaptophosphine oxide compound, an anthraquinone compound, and a biimidazole compound.

作為苯乙酮化合物，可列舉二乙氧基苯乙酮、2-甲基-2-味啉基-1-(4-甲基硫基苯基)丙烷-1-酮、2-二甲基胺基-1-(4-味啉基苯基)-2-苄基丁烷-1-酮、2-二甲基胺基-1-(4-味啉基苯基)-2-(4-甲基苯基甲基)丁烷-1-酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、苯偶醯二甲基縮酮、2-羥基-2-甲基-1-[4-(2-羥基乙氧基)苯基]丙烷-1-酮、1-羥基環己基苯基酮、2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙烷-1-酮之低聚物等，較佳可列舉2-甲基-2-味啉基-1-(4-甲基硫基苯基)丙烷-1-酮、2-二甲基胺基-1-(4-味啉基苯基)-2-苄基丁烷-1-酮等。亦可使用Irgacure 369、907(以上為Ciba Japan公司製造)等市售品。Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propan-1-one, and 2-dimethyl group. Amino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 2-dimethylamino-1-(4-morpholinylphenyl)-2-(4) -methylphenylmethyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin dimethyl ketal, 2-hydroxy-2-methyl 1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-[4-(1- The oligomer of methylvinyl)phenyl]propan-1-one, etc., preferably, 2-methyl-2-sodium benzoyl-1-(4-methylthiophenyl)propane-1- Ketone, 2-dimethylamino-1-(4-morpholinylphenyl)-2-benzylbutane-1-one, and the like. Commercial products such as Irgacure 369 and 907 (above, manufactured by Ciba Japan Co., Ltd.) can also be used.

作為三系化合物，可列舉2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三、2,4-雙(三氯甲基)-6-向日葵基-1,3,5-三、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三等。As three The compound is exemplified by 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-sunflower-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three Wait.

作為醯基氧化膦系起始劑，可列舉2,4,6-三甲基苯甲醯基二苯基氧化膦等。亦可使用Irgacure 819(Ciba Japan公司製造)等市售品。Examples of the thiol phosphine oxide-based initiator include 2,4,6-trimethylbenzimidyldiphenylphosphine oxide. Commercial products such as Irgacure 819 (manufactured by Ciba Japan Co., Ltd.) can also be used.

作為肟化合物，可列舉N-苯甲醯氧基-1-(4-苯基硫基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺、N-乙醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑基-3-基]乙烷-1-亞胺、N-乙醯氧基-1-[9-乙基-6-{2-甲基-4-(3,3-二甲基-2,4-二氧雜環戊基甲氧基)苯甲醯基}-9H-咔唑基-3-基]乙烷-1-亞胺等。亦可使用Irgacure OXE-01、OXE-02(以上為Ciba Japan公司製造)，N-1919(ADEKA公司製造)等市售品。As the hydrazine compound, N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzylideneoxy-1-(4) can be cited. -phenylthiophenyl)octane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzhydryl)-9H- Oxazolyl-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl- 2,4-Dioxalanylmethoxy)benzylidene}-9H-carbazolyl-3-yl]ethane-1-imine and the like. Commercial products such as Irgacure OXE-01, OXE-02 (the above is manufactured by Ciba Japan Co., Ltd.), and N-1919 (made by ADEKA Co., Ltd.) can also be used.

作為聯咪唑化合物，可列舉2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(2,3-二氯苯基)-4,4',5,5'-四苯基聯咪唑(例如參照日本專利特開平6-75372號公報、日本專利特開平6-75373號公報等)、2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(烷氧基苯基)聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(二烷氧基苯基)聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(三烷氧基苯基)聯咪唑(例如參照日本專利特公昭48-38403號公報、日本專利特開昭62-174204號公報等)、4,4',5,5'-位之苯基被羰基烷氧基取代之咪唑化合物(例如參照日本專利特開平7-10913號公報等)等。較佳可列舉2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(2,3-二氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(2,4-二氯苯基)-4,4',5,5'-四苯基聯咪唑。As the biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro) can be mentioned. Phenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, see Japanese Patent Laid-Open No. Hei 6-75372, Japanese Patent Laid-Open No. Hei 6-75373, etc.), 2, 2'-double (2-Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra Alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'- Bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, see Japanese Patent Publication No. Sho 48-38403, Japanese Patent Laid-Open No. 62-- An imidazole compound in which a phenyl group at the 4,4', 5, 5'-position is substituted with a carbonyl alkoxy group (for example, see Japanese Patent Laid-Open Publication No. Hei 7-10913, etc.). Preferably, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl) is exemplified. -4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole.

進而，作為光聚合起始劑(D)，可列舉：安息香、安息香甲醚、安息香***、安息香異丙醚、安息香異丁醚等安息香化合物；二苯甲酮、鄰苯甲醯基苯甲酸甲酯、4-苯基二苯甲酮、4-苯甲醯基-4'-甲基二苯基硫醚、3,3',4,4'-四(第三丁基過氧基羰基)二苯甲酮、2,4,6-三甲基二苯甲酮等二苯甲酮化合物；9,10-菲醌、2-乙基蔥醌、樟腦醌等醌化合物；10-丁基-2-氯吖啶酮、苯偶醯、苯基乙醛酸甲酯、二茂鈦化合物等。該等較佳為與後述之光聚合起始助劑(D1)(特別是胺類)組合使用。Further, examples of the photopolymerization initiator (D) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, benzoyl benzoic acid Ester, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl) Benzophenone compounds such as benzophenone and 2,4,6-trimethylbenzophenone; anthraquinone compounds such as 9,10-phenanthrenequinone, 2-ethyl onion, camphorquinone; 10-butyl- 2-chloroacridone, benzophenone, methyl phenylglyoxylate, titanocene compound, and the like. These are preferably used in combination with a photopolymerization initiation aid (D1) (particularly an amine) to be described later.

作為藉由光而產生酸之酸產生劑，例如可列舉：4-羥基苯基二甲基鋶對甲苯磺酸鹽、4-羥基苯基二甲基鋶六氟銻酸鹽、4-乙醯氧基苯基二甲基鋶對甲苯磺酸鹽、4-乙醯氧基苯基-甲基-苄基鋶六氟銻酸鹽、三苯基鋶對甲苯磺酸鹽、三苯基鋶六氟銻酸鹽、二苯基錪對甲苯磺酸鹽、二苯基錪六氟銻酸鹽等鎓鹽類，或硝基苄基甲苯磺酸酯類，安息香甲苯磺酸酯類等。Examples of the acid generator which generates an acid by light include 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethylhydrazine. Oxyphenyl dimethyl quinone p-toluene sulfonate, 4-ethoxy phenyl phenyl-methyl-benzyl hexafluoroantimonate, triphenyl sulfonium p-toluene sulfonate, triphenyl sulfonium a sulfonium salt such as fluoroantimonate, diphenylphosphonium p-toluenesulfonate or diphenylphosphonium hexafluoroantimonate; or nitrobenzyl tosylate, benzoin tosylate or the like.

光聚合起始劑(D)例如亦可為三化合物般藉由光同時產生活性自由基與酸之化合物。The photopolymerization initiator (D) may be, for example, three Compounds that simultaneously produce active radicals and acids by light.

光聚合起始劑(D)之含量相對於樹脂(B)及光聚合性化合物(C)之合計量較佳為0.1~30質量%，更佳為1~20質量%。The total amount of the photopolymerization initiator (D) is preferably 0.1 to 30% by mass, and more preferably 1 to 20% by mass based on the total amount of the resin (B) and the photopolymerizable compound (C).

若光聚合起始劑之含量在上述範圍內，則感度變高而曝光時間縮短，生產性提高。When the content of the photopolymerization initiator is within the above range, the sensitivity is increased, the exposure time is shortened, and the productivity is improved.

本發明之著色感光性樹脂組合物亦可進而含有光聚合起始助劑(D1)。光聚合起始助劑(D1)通常為與光聚合起始劑(D)組合使用，用於促進由光聚合起始劑引發聚合之光聚合性化合物之聚合的化合物、或增感劑。The colored photosensitive resin composition of the present invention may further contain a photopolymerization initiation aid (D1). The photopolymerization initiation aid (D1) is usually used in combination with a photopolymerization initiator (D) to promote polymerization of a photopolymerizable compound which initiates polymerization by a photopolymerization initiator, or a sensitizer.

作為光聚合起始助劑(D1)，可列舉胺化合物、烷氧基蔥化合物、9-氧硫化合物、羧酸化合物等。As the photopolymerization initiation aid (D1), an amine compound, an alkoxy onion compound, and 9-oxosulfuric acid can be cited. a compound, a carboxylic acid compound or the like.

作為胺化合物，可列舉三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、苯甲酸-2-二甲基胺基乙酯、4-二甲基胺基苯甲酸-2-乙基己酯、N,N-二甲基對甲苯胺、4,4'-雙(二甲基胺基)二苯甲酮(通稱米其勒酮)、4,4'-雙(二乙基胺基)二苯甲酮、4,4'-雙(乙基甲基胺基)二苯甲酮等，其中較佳為4,4'-雙(二乙基胺基)二苯甲酮。亦可使用EAB-F(保土谷化學工業(股)製造)等市售品。Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamine. Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4, 4'-bis(dimethylamino)benzophenone (commonly known as miconesone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethyl Methylamino)benzophenone or the like, of which 4,4'-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

作為烷氧基蔥化合物，可列舉9,10-二甲氧基蔥、2-乙基-9,10-二甲氧基蔥、9,10-二乙氧基蔥、2-乙基-9,10-二乙氧基蔥、9,10-二丁氧基蔥、2-乙基-9,10-二丁氧基蔥等。Examples of the alkoxy onion compound include 9,10-dimethoxy onion, 2-ethyl-9,10-dimethoxy onion, 9,10-diethoxy onion, and 2-ethyl-9. , 10-diethoxy onion, 9,10-dibutoxy onion, 2-ethyl-9,10-dibutoxy onion, and the like.

作為9-氧硫化合物，可列舉2-異丙基-9-氧硫、4-異丙基-9-氧硫、2,4-二乙基-9-氧硫、2,4-二氯-9-氧硫、1-氯-4-丙氧基-9-氧硫等。9-oxosulfur The compound may, for example, be 2-isopropyl-9-oxosulfur 4-isopropyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-dichloro-9-oxosulfur 1-chloro-4-propoxy-9-oxosulfur Wait.

作為羧酸化合物，可列舉苯硫基乙酸、甲基苯硫基乙酸、乙基苯硫基乙酸、甲基乙基苯硫基乙酸、二甲基苯硫基乙酸、甲氧基苯硫基乙酸、二甲氧基苯硫基乙酸、氯苯硫基乙酸、二氯苯硫基乙酸、N-苯基甘胺酸、苯氧基乙酸、萘硫基乙酸、N-萘基甘胺酸、萘氧基乙酸等。Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, and methoxyphenylthioacetic acid. Dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthalene Oxyacetic acid, etc.

光聚合起始助劑(D1)可單獨使用亦可組合使用兩種以上。The photopolymerization initiation aid (D1) may be used alone or in combination of two or more.

於使用該等光聚合起始助劑(D1)時，其使用量相對於光聚合起始劑(D)1莫耳較佳為0.01~10莫耳，更佳為0.01~5莫耳。When the photopolymerization initiation assistant (D1) is used, it is preferably used in an amount of from 0.01 to 10 mols, more preferably from 0.01 to 5 mols, per mol of the photopolymerization initiator (D).

本發明之著色感光性樹脂組合物含有溶劑(E)。The colored photosensitive resin composition of the present invention contains a solvent (E).

溶劑(E)並無特別限定，可使用該領域中通常使用之溶劑。例如可自酯溶劑(含有-COO-之溶劑)、酯溶劑以外之醚溶劑(含有-O-之溶劑)、醚酯溶劑(含有-COO-與-O-之溶劑)、酯溶劑以外之酮溶劑(含有-CO-之溶劑)、醇溶劑、芳香族烴溶劑、醯胺溶劑、二甲基亞碸等中選擇使用。The solvent (E) is not particularly limited, and a solvent which is usually used in the field can be used. For example, it can be used from an ester solvent (a solvent containing -COO-), an ether solvent other than an ester solvent (a solvent containing -O-), an ether ester solvent (a solvent containing -COO- and -O-), and a ketone other than an ester solvent. A solvent (a solvent containing -CO-), an alcohol solvent, an aromatic hydrocarbon solvent, a guanamine solvent, dimethyl hydrazine, etc. are selected and used.

作為酯溶劑，可列舉乳酸甲酯、乳酸乙酯、乳酸丁酯、2-羥基異丁酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲酸戊酯、乙酸異戊酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、環己醇乙酸酯、γ-丁內酯等。Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclohexane Alcohol acetate, γ-butyrolactone and the like.

作為醚溶劑，可列舉乙二醇單甲醚、乙二醇單***、乙二醇單丙醚、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單***、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單***、丙二醇單丙醚、丙二醇單丁醚、3-甲氧基-1-丁醇、3-甲氧基-3-甲基丁醇、四氫呋喃、四氫吡喃、1，4-二烷、二乙二醇二甲醚、二乙二醇二***、二乙二醇甲***、二乙二醇二丙醚、二乙二醇二丁醚、苯甲醚、苯***、甲基苯甲醚等。Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethyl ether. Glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran , tetrahydropyran, 1,4-two Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether, methylbenzene Methyl ether and the like.

作為醚酯溶劑，可列舉甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯、乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、二乙二醇單***乙酸酯、二乙二醇單丁醚乙酸酯等。Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-methoxypropionate. Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate Ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-B Ethyl oxy-2-methylpropanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate Ester and the like.

作為酮溶劑，可列舉4-羥基-4-甲基-2-戊酮、丙酮、2-丁酮、2-庚酮、3-庚酮、4-庚酮、4-甲基-2-戊酮、環戊酮、環己酮、異佛爾酮等。Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2-pentyl Ketone, cyclopentanone, cyclohexanone, isophorone and the like.

作為醇溶劑，可列舉甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇、甘油等。Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

作為芳香族烴溶劑，可列舉苯、甲苯、二甲苯、均三甲苯等。Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

作為醯胺溶劑，可列舉N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮等。Examples of the guanamine solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

該等溶劑可單獨使用或組合使用兩種以上。These solvents may be used alone or in combination of two or more.

上述溶劑中，就塗佈性、乾燥性之方面而言，較佳為1 atm下之沸點為120℃以上、180℃以下之有機溶劑。其中，較佳為丙二醇單甲醚乙酸酯、乳酸乙酯、丙二醇單甲醚、3-乙氧基丙酸乙酯、乙二醇單甲醚、二乙二醇單甲醚、二乙二醇單***、4-羥基-4-甲基-2-戊酮、N,N-二甲基甲醯胺、N-甲基吡咯啶酮等，更佳為丙二醇單甲醚乙酸酯、乳酸乙酯、3-乙氧基丙酸乙酯等。Among the above solvents, in terms of coatability and drying property, an organic solvent having a boiling point of 1 to m of 120 ° C or more and 180 ° C or less is preferable. Among them, preferred are propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene glycol. Alcohol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc., more preferably propylene glycol monomethyl ether acetate, lactic acid Ethyl ester, ethyl 3-ethoxypropionate, and the like.

著色感光性樹脂組合物中之溶劑(E)之含量相對於著色感光性樹脂組合物較佳為70~95質量%，更佳為75~92質量%。換言之，著色感光性樹脂組合物之固體成分較佳為5~30質量%，更佳為8~25質量%。若溶劑(E)之含量在上述範圍內，則有塗佈時之平坦性變良好，且形成彩色濾光片時色濃度不會不足故顯示特性變良好之傾向。The content of the solvent (E) in the coloring photosensitive resin composition is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass based on the coloring photosensitive resin composition. In other words, the solid content of the colored photosensitive resin composition is preferably from 5 to 30% by mass, more preferably from 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color density is not insufficient when the color filter is formed, so that the display characteristics tend to be good.

本發明之著色感光性樹脂組合物中亦可進而含有界面活性劑(F)。作為界面活性劑(F)，可列舉聚矽氧系界面活性劑、氟系界面活性劑及含有氟原子之聚矽氧系界面活性劑等。該等亦可於側鏈上具有聚合性基。The coloring photosensitive resin composition of the present invention may further contain a surfactant (F). Examples of the surfactant (F) include a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based surfactant containing a fluorine atom. These may also have a polymerizable group on the side chain.

作為聚矽氧系界面活性劑，可列舉具有矽氧烷鍵之界面活性劑等。具體可列舉：Toray Silicone DC3PA、Toray Silicone SH7PA、Toray Silicone DC11PA、Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA、Toray Silicone SH30PA、聚醚改性聚矽氧油SH8400(商品名，東麗道康寧(股)製造)，KP321、KP322、KP323、KP324、KP326、KP340、KP341(信越化學工業(股)製造)，TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF-4446、TSF4452、TSF4460(邁圖高新材料日本有限公司(Momentive Performance Materials Japan LLC)製造)等。The polyoxosiloxane surfactant may, for example, be a surfactant having a decane bond. Specific examples include: Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Polyether Modified Polyoxyl SH8400 (trade name, Toray Dow Corning) ))), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Mitto Hi-Tech) Material Japan Co., Ltd. (manufactured by Momentive Performance Materials Japan LLC) and the like.

作為上述氟系界面活性劑，可列舉具有氟碳鏈之界面活性劑等。具體可列舉：Fluorad(商品名)FC430、Fluorad FC431(住友3M(股)製造)，Megaface(商品名)F142D、Megaface F171、Megaface F172、Megaface F173、Megaface F177、Megaface F183、Megaface R30、Megaface RS-718-K(DIC(股)製造)，Eftop(商品名)EF301、Eftop EF303、Eftop EF351、Eftop EF352(三菱材料電子化成(股)製造)，Surflon(商品名)S381、Surflon S382、Surflon SC101、Surflon SC105(旭硝子(股)製造)，E5844(Daikin Fine Chemical研究所(股)製造)等。The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain. Specific examples include: Fluorad (trade name) FC430, Fluorad FC431 (manufactured by Sumitomo 3M), Megaface (trade name) F142D, Megaface F171, Megaface F172, Megaface F173, Megaface F177, Megaface F183, Megaface R30, Megaface RS- 718-K (manufactured by DIC), Eftop (trade name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (trade name) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Research Institute Co., Ltd.), and the like.

作為上述含有氟原子之聚矽氧系界面活性劑，可列舉具有矽氧烷鍵及氟碳鏈之界面活性劑等。具體可列舉Megaface(註冊商標)R08、Megaface BL20、Megaface F475、Megaface F477、Megaface F443(DIC(股)製造)等。The polyfluorene-based surfactant containing a fluorine atom may, for example, be a surfactant having a decane bond or a fluorocarbon chain. Specific examples include Megaface (registered trademark) R08, Megaface BL20, Megaface F475, Megaface F477, and Megaface F443 (manufactured by DIC).

該等界面活性劑可單獨使用亦可組合使用兩種以上。These surfactants may be used alone or in combination of two or more.

界面活性劑(F)之含量相對於著色感光性樹脂組合物較佳為0.001質量%以上、0.2質量%以下，更佳為0.002質量%以上、0.1質量%以下，進而佳為0.01質量%以上、0.05質量%以下。若界面活性劑(F)之含量在上述範圍內，則可使塗膜之平坦性良好。The content of the surfactant (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more, 0.1% by mass or less, and further preferably 0.01% by mass or more, based on the coloring photosensitive resin composition. 0.05% by mass or less. When the content of the surfactant (F) is within the above range, the flatness of the coating film can be improved.

若本發明之著色感光性樹脂組合物為包含著色劑(A)、鹼溶性樹脂(B)、光聚合性化合物(C)、光聚合起始劑(D)、溶劑(E)及界面活性劑(F)者，則塗佈性優異，可獲得耐溶劑性及分光優異之著色圖案。The colored photosensitive resin composition of the present invention contains a coloring agent (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E), and a surfactant. (F) is excellent in coatability, and a coloring pattern excellent in solvent resistance and spectroscopicity can be obtained.

作為使用本發明之著色感光性樹脂組合物形成著色圖案之方法，例如可列舉：將本發明之著色感光性樹脂組合物塗佈於基板或其他樹脂層(例如先形成於基板上之其他著色感光性樹脂組合物層等)上，將溶劑等揮發成分去除/乾燥而形成著色層，經由光罩對該著色層曝光，進行顯影之方法；使用不需要光微影法之噴墨機器之方法等。As a method of forming a colored pattern by using the colored photosensitive resin composition of the present invention, for example, the colored photosensitive resin composition of the present invention is applied to a substrate or another resin layer (for example, other colored photosensitive materials formed on the substrate first). The resin composition layer or the like is obtained by removing/drying a volatile component such as a solvent to form a colored layer, exposing the colored layer to a colored layer via a photomask, and developing the inkjet device without using a photolithography method. .

此時之塗膜之膜厚並無特別限定，可根據所使用之材料、用途等而適當調整，通常為0.1~30 μm，較佳為1~20 μm，更佳為1~6 μm。The film thickness of the coating film at this time is not particularly limited, and may be appropriately adjusted depending on the material to be used, the use, and the like, and is usually 0.1 to 30 μm, preferably 1 to 20 μm, and more preferably 1 to 6 μm.

著色感光性樹脂組合物之塗佈方法例如可列舉：擠壓塗佈法、直接凹版塗佈法、反向凹版塗佈法、CAP(capillary，毛細管)塗佈法、模塗佈法等。又，亦可使用浸漬塗佈機、棒塗佈機、旋轉塗佈機、狹縫旋轉塗佈機、狹縫塗佈機(有時亦稱為模塗佈機、淋幕式塗佈機、非旋轉塗佈機)等塗佈機進行塗佈。Examples of the coating method of the colored photosensitive resin composition include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP (capillary) coating method, and a die coating method. Further, a dip coater, a bar coater, a spin coater, a slit spin coater, or a slit coater (also sometimes referred to as a die coater or a curtain coater) may be used. Coating by a coater such as a non-rotating coater.

溶劑之去除/乾燥例如可列舉自然乾燥、通風乾燥、減壓乾燥、加熱乾燥等。具體之乾燥溫度較佳為10~120℃，更佳為25~100℃。乾燥時間較佳為10秒鐘~60分鐘，更佳為30秒鐘~30分鐘。減壓乾燥較佳為於50~150 Pa之壓力下、於20~25℃之範圍內進行。Examples of the removal/drying of the solvent include natural drying, air drying, reduced pressure drying, and heat drying. The specific drying temperature is preferably from 10 to 120 ° C, more preferably from 25 to 100 ° C. The drying time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes. The drying under reduced pressure is preferably carried out at a pressure of 50 to 150 Pa in the range of 20 to 25 °C.

乾燥後之塗膜係介隔用以形成目標圖案之光罩進行曝光。此時之光罩上之圖案形狀並無特別限定，可使用與目標用途相對應之圖案形狀。The dried coating film is exposed through a reticle for forming a target pattern. The shape of the pattern on the photomask at this time is not particularly limited, and a pattern shape corresponding to the intended use can be used.

作為曝光時所使用之光源，較佳為產生250~450 nm之波長之光之光源。具體可列舉水銀燈、發光二極體、金屬鹵化物燈、鹵素燈等，亦可使用截止特定波長域之濾波器進行截止，或使用掠取特定波長域之帶通濾波器選擇性地掠取而進行曝光。As the light source used for the exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. Specific examples thereof include a mercury lamp, a light-emitting diode, a metal halide lamp, a halogen lamp, etc., and may be cut off using a filter that cuts off a specific wavelength range, or selectively extracted by a band pass filter that sweeps a specific wavelength range. .

較佳為使用光罩對準曝光機、步進機等裝置，其原因在於，可對整個曝光面均勻地照射平行光線，或進行光罩與基材之準確之對位。It is preferable to use a mask to align the exposure machine, the stepper, and the like because the entire exposure surface can be uniformly irradiated with parallel rays or the alignment of the mask and the substrate can be accurately performed.

藉由在曝光後使與顯影液接觸之預定部分例如未曝光部溶解而進行顯影，可獲得圖案。作為顯影液，可列舉可含有界面活性劑之鹼性化合物(氫氧化鉀、碳酸鈉、氫氧化四甲基銨等)之水溶液等。The pattern can be obtained by performing development by dissolving a predetermined portion, for example, an unexposed portion, which is in contact with the developer after the exposure. The developing solution may, for example, be an aqueous solution of a basic compound (potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide or the like) which may contain a surfactant.

顯影方法可為攪練法、浸漬法、噴射法等之任一種。進而，顯影時亦可將基板傾斜任意角度。顯影後較佳為進行水洗。The developing method may be any one of a scouring method, a dipping method, a spraying method, and the like. Further, the substrate can be tilted at an arbitrary angle during development. It is preferred to carry out water washing after development.

進而，視需要亦可進行後烘烤。後烘烤較佳為150~230℃、10~240分鐘之範圍。Further, post-baking can be performed as needed. The post-baking is preferably in the range of 150 to 230 ° C for 10 to 240 minutes.

根據本發明，可形成耐溶劑性較高之著色硬化物(例如著色塗膜、著色圖案)，可獲得含有其之高品質之彩色濾光片。According to the present invention, it is possible to form a colored cured product (for example, a colored coating film or a colored pattern) having high solvent resistance, and a high-quality color filter containing the same can be obtained.

本發明之著色感光性樹脂組合物可獲得色濃度、亮度、對比度、感度、解析度、耐熱性等良好之著色圖案及彩色濾光片。又，可以公知之態樣用於具備該等彩色濾光片或著色圖案作為其構成零件之一部分的顯示裝置、例如公知之液晶顯示裝置、有機EL(Electroluminescence，電致發光)裝置、固體攝像元件等各種與著色圖像有關之所有機器。The colored photosensitive resin composition of the present invention can obtain a colored pattern and a color filter which are excellent in color density, brightness, contrast, sensitivity, resolution, heat resistance and the like. Moreover, a display device including such a color filter or a colored pattern as a part of the constituent parts, for example, a known liquid crystal display device, an organic EL (Electroluminescence) device, and a solid-state imaging device can be used. All kinds of machines related to coloring images.

實施例Example

以下，藉由實施例對本發明之著色感光性樹脂組合物加以更詳細說明。Hereinafter, the colored photosensitive resin composition of the present invention will be described in more detail by way of examples.

例中之「%」及「份」只要無特別說明，則為質量%及質量份。In the examples, "%" and "parts" are % by mass and parts by mass unless otherwise specified.

(合成例1)(Synthesis Example 1) <化合物(1-1)之合成><Synthesis of Compound (1-1)>

於2-胺基-4-硝基苯酚(和光純藥工業(股)製造)7.7份中添加水75份後，添加氫氧化鈉2.0份使其溶解。於冰浴冷卻下添加35%亞硝酸鈉(和光純藥工業(股)製造)水溶液9.5份，繼而一點點地添加35%鹽酸30.0份並使其溶解，攪拌2小時，獲得含有重氮鎓鹽之懸浮液。繼而，緩緩添加使醯胺硫酸(和光純藥工業(股)製造)8.9份溶解於水36份中之水溶液，消耗過剩之亞硝酸鈉。After adding 75 parts of water to 7.7 parts of 2-amino-4-nitrophenol (manufactured by Wako Pure Chemical Industries, Ltd.), 2.0 parts of sodium hydroxide was added thereto to dissolve. 9.5 parts of an aqueous solution of 35% sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) was added under ice-cooling, and then 30.0 parts of 35% hydrochloric acid was added little by little and dissolved, and stirred for 2 hours to obtain a salt containing diazonium. Suspension. Then, an aqueous solution in which 8.9 parts of decylamine sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 36 parts of water was slowly added, and excess sodium nitrite was consumed.

繼而，使3-甲基-1-(3'-胺磺醯基苯基)-5-吡唑啉酮(和光純藥工業(股)製造)13份懸浮於水100份中，使用氫氧化鈉將pH值調整為8.0。向其中一邊用15分鐘滴加上述含有重氮鎓鹽之懸浮液，一邊以將pH值控制於7至7.5之範圍內之方式適當追加10%氫氧化鈉溶液。滴加結束後，進一步攪拌30分鐘，由此獲得黃色之懸浮液。攪拌1小時。將過濾所得之黃色固體於減壓下、60℃下乾燥，獲得式(p-1)所示化合物17.9份(產率為85%)。Then, 13 parts of 3-methyl-1-(3'-aminosulfonylphenyl)-5-pyrazolone (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in 100 parts of water, and hydroxide was used. Sodium adjusted the pH to 8.0. To the above, the suspension containing the diazonium salt was added dropwise thereto for 15 minutes, and a 10% sodium hydroxide solution was appropriately added so as to control the pH in the range of 7 to 7.5. After the completion of the dropwise addition, the mixture was further stirred for 30 minutes, whereby a yellow suspension was obtained. Stir for 1 hour. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 17.9 parts of the compound of formula (p-1) (yield: 85%).

將式(p-1)之化合物10份加入至二甲基甲醯胺(東京化成工業(股)製造)100份中並溶解，添加硫酸銨鉻(III)十二水合物(和光純藥工業(股)製造)3.1份、乙酸鈉(和光純藥工業(股)製造)1.1份後，加熱回流4.5小時。冷卻至室溫後，將反應溶液注入至20%食鹽水1500份中，將過濾後所得之橙紅色固體於60℃下乾燥，獲得式(z-1)所示化合物12.8份(60%)。10 parts of the compound of the formula (p-1) was added to 100 parts of dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) and dissolved, and ammonium sulfate (III) dodecahydrate was added (Wako Pure Chemical Industries, Ltd.) (manufactured) (3.1 parts), 1.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), and heated under reflux for 4.5 hours. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% saline, and the orange-red solid obtained after filtration was dried at 60 ° C to obtain 12.8 parts (60%) of the compound of the formula (z-1).

於若丹明B(東京化成工業(股)製造)18份中添加無水氯仿(關東化學(股)製造)170份、樟腦磺酸(Aldrich(股)製造)1.0份、4-(N,N-二甲基胺基)吡啶(東京化成工業(股)製造)1.4份、三乙二醇(和光純藥工業(股)製造)18份並攪拌約30分鐘。其後，緩緩添加於1-乙基-3-(3-二甲基胺基丙基)碳二醯亞胺鹽酸鹽(和光純藥工業(股)製造)10.5份中添加無水氯仿47份預先溶解而成之溶液後，於室溫下攪拌約2小時。以1 N鹽酸水溶液150份進行分液操作2次，然後以10%食鹽水150份將有機層清洗2次。繼而添加無水硫酸鎂43份並攪拌約30分鐘後，過濾乾燥劑，將溶劑蒸餾去除，藉此獲得式(g-1)所示化合物20.6份(產率為90%)。式(g-1)所示化合物之鑑定170 parts of anhydrous chloroform (manufactured by Kanto Chemical Co., Ltd.), camphor sulfonic acid (manufactured by Aldrich Co., Ltd.), 1.0 part, 4-(N, N) were added to 18 parts of Rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd.). -1 parts of dimethylamino)pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.), 18 parts of triethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) and stirred for about 30 minutes. Thereafter, anhydrous chloroform 47 was added to 10.5 parts of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.). After pre-dissolving the solution, it was stirred at room temperature for about 2 hours. The liquid separation operation was carried out twice with 150 parts of a 1 N aqueous hydrochloric acid solution, and then the organic layer was washed twice with 150 parts of 10% saline. Then, after adding 43 parts of anhydrous magnesium sulfate and stirring for about 30 minutes, the desiccant was filtered, and the solvent was distilled off, thereby obtaining 20.6 parts of the compound of the formula (g-1) (yield 90%). Identification of compounds represented by formula (g-1)

(質量分析)離子化模式=ESI+：m/z=575.3[M-Cl- ]+ Exact Mass：610.3(mass analysis) ionization mode = ESI +: m / z = 575.3 [M - Cl - ] + Exact Mass: 610.3

於式(z-1)所示化合物253份中添加甲醇4030份而製備溶液(s1)。又，於式(g-1)所示化合物153份中添加甲醇1080份而製備溶液(t1)。其後於室溫下將溶液(s1)與溶液(t1)混合，攪拌約1小時。將所生成之紅色固體於減壓下、60℃下乾燥，以水3500份清洗後進行過濾，於60℃下減壓乾燥，獲得式(1-1)所示化合物(染料A1)263份(產率為65%)。A solution (s1) was prepared by adding 4030 parts of methanol to 253 parts of the compound represented by the formula (z-1). Further, 1080 parts of methanol was added to 153 parts of the compound represented by the formula (g-1) to prepare a solution (t1). Thereafter, the solution (s1) was mixed with the solution (t1) at room temperature, and stirred for about 1 hour. The resulting red solid was dried under reduced pressure at 60 ° C, washed with water (3500 parts), filtered, and dried under reduced pressure at 60 ° C to obtain 263 parts of the compound of formula (1-1) (dye A1) ( The yield was 65%).

式(1-1)所示化合物之結構係藉由元素分析而確定。分析機器係使用ICP(Inductively Coupled Plasma，感應耦合電漿)發光分析裝置(ICPS-8100，島津製作所(股)製造)。The structure of the compound represented by the formula (1-1) is determined by elemental analysis. The analysis apparatus was an ICP (Inductively Coupled Plasma) luminescence analyzer (ICPS-8100, manufactured by Shimadzu Corporation).

(合成例2)(Synthesis Example 2) <化合物(1-2)之合成><Synthesis of Compound (1-2)>

於若丹明B(東京化成工業(股)製造)5.0份中添加無水氯仿(關東化學(股)製造)40份、樟腦磺酸(Aldrich(股)製造)0.3份、4-(N,N-二甲基胺基)吡啶(東京化成工業(股)製造)0.3份、二乙二醇(和光純藥工業(股)製造)3.9份並攪拌約30分鐘。然後，緩緩添加於1-乙基-3-(3-二甲基胺基丙基)碳二醯亞胺鹽酸鹽(和光純藥工業(股)製造)2.9份中預先添加無水氯仿10份預先溶解而成之溶液後，於室溫下攪拌約2小時。以1 N鹽酸水溶液100份進行2次分液操作後，以10%食鹽水100份將有機層清洗2次。繼而添加無水硫酸鎂12份並攪拌約30分鐘後，過濾乾燥劑並將溶劑蒸餾去除，藉此獲得式(g-2)所示化合物5.0份(產率為85%)。式(g-2)所示化合物之鑑定40 parts of anhydrous chloroform (manufactured by Kanto Chemical Co., Ltd.), camphorsulfonic acid (manufactured by Aldrich Co., Ltd.), 0.3 parts, 4-(N, N) were added to 5.0 parts of Rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd.). - dimethylamino)pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.3 parts, 3.9 parts of diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) and stirred for about 30 minutes. Then, chloroform 10 was added in advance to 2.9 parts of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.). After pre-dissolving the solution, it was stirred at room temperature for about 2 hours. After the liquid separation operation was carried out twice with 100 parts of 1 N aqueous hydrochloric acid solution, the organic layer was washed twice with 100 parts of 10% saline. Then, 12 parts of anhydrous magnesium sulfate was added and stirred for about 30 minutes, and the desiccant was filtered and the solvent was distilled off, whereby 5.0 parts of the compound of the formula (g-2) (yield: 85%) was obtained. Identification of compounds represented by formula (g-2)

(質量分析)離子化模式=ESI+：m/z=531.3[M-Cl- ]+ Exact Mass：566.3(mass analysis) ionization mode = ESI+: m/z = 531.3 [M-Cl - ] + Exact Mass: 566.3

於式(z-1)所示化合物10份中添加N-甲基吡咯啶酮100份而製備溶液(s2)。又，於式(g-2)所示化合物5.6份中添加N-甲基吡咯啶酮50份而製備溶液(t2)。其後於室溫下將溶液(s2)與溶液(t2)混合，攪拌約1小時後，注入至水500份。將所生成之紅色固體過濾並於減壓下、60℃下乾燥，藉此獲得式(1-2)所示化合物(染料A2)15份(產率為95%)。A solution (s2) was prepared by adding 100 parts of N-methylpyrrolidone to 10 parts of the compound of the formula (z-1). Further, 50 parts of N-methylpyrrolidone was added to 5.6 parts of the compound represented by the formula (g-2) to prepare a solution (t2). Thereafter, the solution (s2) was mixed with the solution (t2) at room temperature, and after stirring for about 1 hour, it was poured into 500 parts of water. The resulting red solid was filtered and dried under reduced pressure at 60 ° C, whereby 15 parts of the compound (yield A2) of the formula (1-2) (yield 95%) was obtained.

式(1-1)所示化合物之結構係藉由元素分析而確定。分析機器係使用ICP發光分析裝置(ICPS-8100，島津製作所(股)製造)。The structure of the compound represented by the formula (1-1) is determined by elemental analysis. The analysis machine was an ICP luminescence analyzer (ICPS-8100, manufactured by Shimadzu Corporation).

(合成例3)(Synthesis Example 3) <化合物(1-3)之合成><Synthesis of Compound (1-3)>

藉由與合成例1相同之方法由式(rh-1)所示化合物獲得式(g-3)所示化合物。進而，藉由與合成例1相同之方法獲得式(1-3)所示化合物(染料A3)。The compound of the formula (g-3) was obtained from the compound of the formula (rh-1) by the same method as in the synthesis example 1. Further, a compound represented by the formula (1-3) (dye A3) was obtained by the same method as in Synthesis Example 1.

(合成例4)(Synthesis Example 4) <樹脂溶液B1之合成><Synthesis of Resin Solution B1>

於具備攪拌機、溫度計、回流冷凝器及滴液漏斗之燒瓶內以0.02 L/分鐘流入氮氣而調整成氮氣環境，加入乳酸乙酯305質量份，一邊攪拌一邊加熱至70℃。繼而，溶解於甲基丙烯酸60質量份、3,4-環氧三環[5.2.1.02.6 ]癸基丙烯酸酯(將下述式(I-1)所示化合物及式(II-1)所示化合物以莫耳比50：50混合)240質量份、及乳酸乙酯140質量份中而製備溶液，使用滴液漏斗用4小時將該溶解液滴加至將溫度保持於70℃之燒瓶內。另一方面，使用其他滴液漏斗用4小時將使聚合起始劑2,2'-偶氮雙(2,4-二甲基戊腈)30質量份溶解於乳酸乙酯225質量份中而成之溶液滴加至燒瓶內。聚合起始劑溶液滴加結束後，於70℃保持4小時，其後冷卻至室溫，獲得重量平均分子量Mw為1.3×104 、固體成分為33質量%、酸值為34 mg-KOH/g(溶液)之樹脂溶液B1。In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen gas was introduced at 0.02 L/min to adjust to a nitrogen atmosphere, and 305 parts by mass of ethyl lactate was added thereto, and the mixture was heated to 70 ° C while stirring. Then, it is dissolved in 60 parts by mass of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 2.6 ]decyl acrylate (the compound represented by the following formula (I-1) and the formula (II-1) A solution was prepared by mixing 240 parts by mass of a molar ratio of 50:50 with 140 parts by mass of ethyl lactate, and the solution was added dropwise to a flask maintained at 70 ° C for 4 hours using a dropping funnel. . On the other hand, 30 parts by mass of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts by mass of ethyl lactate using another dropping funnel over 4 hours. The resulting solution was added dropwise to the flask. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 1.3 × 10 4 , a solid content of 33% by mass, and an acid value of 34 mg-KOH / G (solution) resin solution B1.

(合成例5)(Synthesis Example 5) <樹脂溶液B2之合成><Synthesis of Resin Solution B2>

於具備攪拌機、溫度計、回流冷凝器、滴液漏斗及氣體導入管之燒瓶中導入丙二醇單甲醚乙酸酯300質量份。其後，使用氣體導入管將氮氣導入至燒瓶內，將燒瓶內環境置換成氮氣。其後，將燒瓶內之溶液升溫至100℃後，使用滴液漏斗用2小時將包含甲基丙烯酸苄酯176.2質量份、甲基丙烯酸30.2質量份、偶氮雙異丁腈3.6質量份及丙二醇單甲醚乙酸酯197質量份之混合物滴加至燒瓶中，滴加結束後進一步於100℃下繼續攪拌2.5小時，獲得重量平均分子量Mw為9.8×103 、固體成分為34質量%、酸值為102 mg-KOH/g(固體成分換算)之樹脂溶液B2。300 parts by mass of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a gas introduction tube. Thereafter, nitrogen gas was introduced into the flask using a gas introduction tube, and the atmosphere inside the flask was replaced with nitrogen. Thereafter, the solution in the flask was heated to 100 ° C, and then 176.2 parts by mass of benzyl methacrylate, 30.2 parts by mass of methacrylic acid, 3.6 parts by mass of azobisisobutyronitrile, and propylene glycol were contained in a dropping funnel over 2 hours. A mixture of 197 parts by mass of monomethyl ether acetate was added dropwise to the flask, and further stirred at 100 ° C for 2.5 hours after the completion of the dropwise addition to obtain a weight average molecular weight Mw of 9.8 × 10 3 , a solid content of 34% by mass, and an acid. The resin solution B2 was a value of 102 mg-KOH/g (solid content conversion).

(合成例6)(Synthesis Example 6) <樹脂溶液B3之合成><Synthesis of Resin Solution B3>

於具備攪拌機、溫度計、回流冷卻管、滴液漏斗及氣體導入管之燒瓶中導入丙二醇單甲醚乙酸酯333 g。其後，通過氣體導入管將氮氣導入至燒瓶內，將燒瓶內環境置換成氮氣。其後，將燒瓶內之溶液升溫至100℃後，使用滴液漏斗用2小時將包含N-苄基順丁烯二醯亞胺18.7 g、甲基丙烯酸苄酯70.5 g、甲基丙烯酸51.7 g、甲基丙烯酸甲酯90.0 g、偶氮雙異丁腈5.2 g及丙二醇單甲醚乙酸酯182 g之混合物滴加至燒瓶中，滴加結束後進一步於100℃下繼續攪拌5小時。333 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a gas introduction tube. Thereafter, nitrogen gas was introduced into the flask through a gas introduction tube, and the atmosphere inside the flask was replaced with nitrogen. Thereafter, the solution in the flask was heated to 100 ° C, and then 18.7 g of N-benzyl maleimide, 70.5 g of benzyl methacrylate, and 51.7 g of methacrylic acid were contained using a dropping funnel over 2 hours. A mixture of methyl methacrylate 90.0 g, azobisisobutyronitrile 5.2 g, and propylene glycol monomethyl ether acetate 182 g was added dropwise to the flask, and after the completion of the dropwise addition, stirring was further continued at 100 ° C for 5 hours.

攪拌結束後，通過氣體導入管將空氣導入至燒瓶內，將燒瓶內環境置換成空氣後，將甲基丙烯酸縮水甘油酯28.5 g、三(二甲基胺基)甲基苯酚1.3 g及對苯二酚0.165 g投入至燒瓶內，於110℃下繼續反應6小時，獲得重量平均分子量Mw為16×103 、固體成分為31%、酸值為80 mg-KOH/g(固體成分換算)之樹脂溶液B3。After the completion of the stirring, air was introduced into the flask through a gas introduction tube, and the environment inside the flask was replaced with air, and then 28.5 g of glycidyl methacrylate, 1.3 g of tris(dimethylamino)methylphenol, and p-toluene were added. 0.165 g of diphenol was placed in a flask, and the reaction was continued at 110 ° C for 6 hours to obtain a weight average molecular weight Mw of 16 × 10 3 , a solid content of 31%, and an acid value of 80 mg-KOH/g (in terms of solid content). Resin solution B3.

關於上述樹脂之聚苯乙烯換算重量平均分子量之測定，係使用GPC(Gel Permeation Chromatography[，凝膠滲透層析]法於以下條件下進行。The measurement of the polystyrene-equivalent weight average molecular weight of the above resin was carried out under the following conditions using a GPC (Gel Permeation Chromatography) method.

裝置：HLC-8120GPC(東曹(股)製造)Device: HLC-8120GPC (made by Tosoh Co., Ltd.)

管柱：TSK-GELG2000HXLColumn: TSK-GELG2000HXL

管柱溫度：40℃Column temperature: 40 ° C

溶劑：THF(Tetrahydrofuran，四氫呋喃)Solvent: THF (Tetrahydrofuran, tetrahydrofuran)

流速：1.0 mL/minFlow rate: 1.0 mL/min

受檢液固體成分濃度：0.001~0.01%Solid concentration of the test liquid: 0.001~0.01%

注入量：50 μLInjection volume: 50 μL

檢測器：RI(Refractive Index，折射率)Detector: RI (Refractive Index, refractive index)

校正用標準物質：TSK STANDARD POLYSTYRENEStandard material for calibration: TSK STANDARD POLYSTYRENE

F-40、F-4、F-1、A-2500、A-500(東曹(股)製造)F-40, F-4, F-1, A-2500, A-500 (made by Tosoh Co., Ltd.)

(實施例1)(Example 1) [著色感光性樹脂組合物1之製備][Preparation of Colored Photosensitive Resin Composition 1]

混合，使用珠磨機使顏料充分地分散，繼而混合Mix and use a bead mill to fully disperse the pigment and then mix

而獲得著色感光性樹脂組合物1。The colored photosensitive resin composition 1 was obtained.

[圖案之形成][Formation of patterns]

於2吋見方之玻璃基板(Eagle 2000，Corning公司製造)上利用旋轉塗佈法塗佈著色感光性樹脂組合物1後，於100℃下預烘烤3分鐘。冷卻後，將該塗佈有著色感光性樹脂組合物1之基板與石英玻璃製光罩之間隔設為100 μm，使用曝光機(TME-150RSK，Topcon(股)製造)於大氣環境下以80 mJ/cm2 之曝光量(365 nm基準)進行光照射。又，作為光罩，使用形成有100 μm之線與間隙圖案者。光照射後，使該基板於含有非離子系界面活性劑0.12%與氫氧化鉀0.04%之水溶液中於23℃下浸漬80秒鐘進行顯影，水洗後，於烘箱中於230℃下進行30分鐘後烘烤。放置冷卻後，使用膜厚測定裝置(DEKTAK3，日本真空技術(股)製造))測定所得著色圖案之膜厚，結果為2.0 μm。The colored photosensitive resin composition 1 was applied by a spin coating method on a glass substrate (Eagle 2000, manufactured by Corning Co., Ltd.), and then prebaked at 100 ° C for 3 minutes. After cooling, the distance between the substrate coated with the colored photosensitive resin composition 1 and the mask made of quartz glass was set to 100 μm, and an exposure machine (TME-150RSK, manufactured by Topcon) was used in an atmosphere of 80 Å. The exposure amount of mJ/cm 2 (365 nm reference) was irradiated with light. Further, as the photomask, a line and a gap pattern formed with 100 μm were used. After the light irradiation, the substrate was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C for 80 seconds for development, washed with water, and then baked in an oven at 230 ° C for 30 minutes. After baking. After the film was allowed to stand for cooling, the film thickness of the obtained colored pattern was measured using a film thickness measuring device (DEKTAK3, manufactured by Nippon Vacuum Technology Co., Ltd.), and it was 2.0 μm.

[耐溶劑性評價][Solvent resistance evaluation]

上述圖案形成中，除了不使用光罩進行曝光以外進行同樣之操作，製作著色塗膜。將所得塗膜於23℃之N-甲基-2-吡咯啶酮中浸漬30分鐘，使用測色機(OSP-SP-200，Olympus(股)製造)測定分光，使用C光源之等色函數測定CIE(Commission internationale de l'clairage，國際照明委員會)之XYZ表色系統中之浸漬前後之xy色度座標(Rx，Ry)(即色度)及亮度RY，計算浸漬前後之色差ΔEab＊。若ΔEab＊為2以下，則可判斷為耐溶劑性良好。結果示於表1中。In the pattern formation described above, the same operation was carried out except that the exposure was not performed using a photomask, and a colored coating film was produced. The obtained coating film was immersed in N-methyl-2-pyrrolidone at 23 ° C for 30 minutes, and the spectroscopic measurement was carried out using a color measuring machine (OSP-SP-200, manufactured by Olympus Co., Ltd.) using an isochromatic function of a C light source. Determination of CIE (Commission internationale de l' Clairage, International Commission on Illumination) The XY chromaticity coordinates (Rx, Ry) (ie, chromaticity) and brightness RY before and after immersion in the XYZ color system are used to calculate the color difference ΔEab* before and after immersion. When ΔEab* is 2 or less, it can be judged that solvent resistance is good. The results are shown in Table 1.

(實施例2)(Example 2)

除了將染料A1換成染料A2以外，與實施例1同樣地獲得著色感光性樹脂組合物2。與實施例1同樣地對著色感光性樹脂組合物2進行評價。結果示於表1中。The colored photosensitive resin composition 2 was obtained in the same manner as in Example 1 except that the dye A1 was changed to the dye A2. The colored photosensitive resin composition 2 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(實施例3)(Example 3)

除了將染料A1換成染料A3以外，與實施例1同樣地獲得著色感光性樹脂組合物3。對著色感光性樹脂組合物3與實施例1同樣地進行評價，結果可獲得良好之耐溶劑性。The colored photosensitive resin composition 3 was obtained in the same manner as in Example 1 except that the dye A1 was changed to the dye A3. When the colored photosensitive resin composition 3 was evaluated in the same manner as in Example 1, good solvent resistance was obtained.

(實施例4)(Example 4)

混合，使用珠磨機使顏料充分地分散，獲得分散體a。The mixture was mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a dispersion a.

混合，使用珠磨機使顏料充分地分散後，與分散體a混合，進而混合Mixing, using a bead mill to fully disperse the pigment, mixing with the dispersion a, and then mixing

而獲得著色感光性樹脂組合物4。對著色感光性樹脂組合物4與實施例1同樣地進行評價。結果示於表1中。The colored photosensitive resin composition 4 was obtained. The colored photosensitive resin composition 4 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(實施例5)(Example 5)

混合，使用珠磨機使顏料充分地分散，繼而混合Mix and use a bead mill to fully disperse the pigment and then mix

而獲得著色感光性樹脂組合物5。與實施例1同樣地對著色感光性樹脂組合物5進行評價。結果示於表1中。The colored photosensitive resin composition 5 was obtained. The colored photosensitive resin composition 5 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(實施例6)(Example 6)

混合，使用珠磨機使顏料充分地分散，獲得分散體b。The mixture was mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a dispersion b.

混合，使用珠磨機使顏料充分地分散後，與分散體b混合，繼而，混合Mixing, using a bead mill to fully disperse the pigment, mixing with the dispersion b, and then mixing

而獲得著色感光性樹脂組合物6。與實施例1同樣地對著色感光性樹脂組合物6進行評價。結果示於表1中。The colored photosensitive resin composition 6 was obtained. The colored photosensitive resin composition 6 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(比較例1)(Comparative Example 1)

混合而獲得著色感光性樹脂組合物7，與實施例1同樣地著色感光性樹脂組合物7進行評價。結果示於表1中。The colored photosensitive resin composition 7 was obtained by mixing, and the photosensitive resin composition 7 was colored and evaluated similarly to Example 1. The results are shown in Table 1.

(比較例2)(Comparative Example 2)

混合而獲得著色感光性樹脂組合物8。與實施例1同樣地對著色感光性樹脂組合物8進行評價。結果示於表1中。The colored photosensitive resin composition 8 was obtained by mixing. The colored photosensitive resin composition 8 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

＊)於N-甲基-2-吡咯啶酮浸漬過程中著色塗膜自玻璃基板剝離，故無法測定色差ΔEab＊。*) The colored coating film was peeled off from the glass substrate during the impregnation of N-methyl-2-pyrrolidone, so the color difference ΔEab* could not be measured.

(合成例7)(Synthesis Example 7) <化合物(1-23)之合成><Synthesis of Compound (1-23)>

於2-胺基-4-甲基磺醯胺-6-硝基苯酚(CAS No. 101861-04-5)7.5份中添加水65份後，添加氫氧化鈉1.3份並使其溶解。於冰浴冷卻下添加35%亞硝酸鈉(和光純藥工業(股)製造)水溶液6.1份，繼而一點點地添加35%鹽酸19.4份並使其溶解，攪拌2小時，獲得含有重氮鎓鹽之懸浮液。繼而，緩緩添加使醯胺硫酸(和光純藥工業(股)製造)5.6份溶解於水26份中而成之水溶液，消耗過剩之亞硝酸鈉。After adding 65 parts of water to 7.5 parts of 2-amino-4-methylsulfonamide-6-nitrophenol (CAS No. 101861-04-5), 1.3 parts of sodium hydroxide was added and dissolved. 6.1 parts of an aqueous solution of 35% sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) was added under cooling in an ice bath, and then 19.4 parts of 35% hydrochloric acid was added little by little and dissolved, and stirred for 2 hours to obtain a salt containing diazonium. Suspension. Then, an aqueous solution obtained by dissolving 5.6 parts of decylamine sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) in 26 parts of water was gradually added, and excess sodium nitrite was consumed.

繼而，使3-甲基-1-苯基-5-吡唑啉酮(和光純藥工業(股)製造)5.6份懸浮於水70份中，使用氫氧化鈉將pH值調整為8.0。向其中一邊用15分鐘滴加上述含有重氮鎓鹽之懸浮液，一邊以將pH值控制於7至7.5之範圍內之方式適當追加10%氫氧化鈉溶液。滴加結束後，進一步攪拌30分鐘，由此獲得黃色之懸浮液。攪拌1小時。將過濾所得之黃色固體於減壓下、60℃下加以乾燥，獲得式(p-2)所示化合物11.7份(產率為87%)。Then, 5.6 parts of 3-methyl-1-phenyl-5-pyrazolone (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in 70 parts of water, and the pH was adjusted to 8.0 using sodium hydroxide. To the above, the suspension containing the diazonium salt was added dropwise thereto for 15 minutes, and a 10% sodium hydroxide solution was appropriately added so as to control the pH in the range of 7 to 7.5. After the completion of the dropwise addition, the mixture was further stirred for 30 minutes, whereby a yellow suspension was obtained. Stir for 1 hour. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 11.7 parts of the compound of formula (p-2) (yield: 87%).

將式(p-2)之化合物10份加入至二甲基甲醯胺(東京化成工業(股)製造)100份中並溶解，添加硫酸銨鉻(III)十二水合物(和光純藥工業(股)製造)3.1份、乙酸鈉(和光純藥工業(股)製造)1.1份後，加熱回流4.5小時。冷卻至室溫後，將反應溶液注入至20%食鹽水1500份中，將過濾後所得之橙紅色固體於60℃下乾燥，獲得式(z-2)所示化合物13.6份(63%)。10 parts of the compound of the formula (p-2) was added to 100 parts of dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) and dissolved, and ammonium sulfate (III) dodecahydrate was added (Wako Pure Chemical Industries, Ltd.) (manufactured) (3.1 parts), 1.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), and heated under reflux for 4.5 hours. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% saline, and the orange-red solid obtained after filtration was dried at 60 ° C to obtain 13.6 parts (63%) of the compound of the formula (z-2).

式(z-2)所示化合物之鑑定Identification of compounds represented by formula (z-2)

(質量分析)離子化模式=ESI-：m/z=882.1[M-Na+ ]- Exact Mass：905.1(mass analysis) ionization mode = ESI-: m/z = 882.1 [M-Na + ] - Exact Mass: 905.1

於式(z-2)所示化合物253份中添加甲醇4030份而製備溶液(s3)。又，於式(g-1)所示化合物153份中添加甲醇1080份而製備溶液(t3)。其後於室溫下將溶液(s3)與溶液(t3)混合，攪拌約1小時。將所生成之紅色固體於減壓下、60℃下乾燥，以水3500份清洗後進行過濾，於60℃下進行減壓乾燥，獲得式(1-23)所示化合物(染料A4)263份(產率為65%)。A solution (s3) was prepared by adding 4030 parts of methanol to 253 parts of the compound represented by the formula (z-2). Further, 1080 parts of methanol was added to 153 parts of the compound represented by the formula (g-1) to prepare a solution (t3). Thereafter, the solution (s3) was mixed with the solution (t3) at room temperature, and stirred for about 1 hour. The resulting red solid was dried under reduced pressure at 60 ° C, washed with water (3500 parts), filtered, and dried under reduced pressure at 60 ° C to obtain 263 parts of the compound of formula (1-23) (dye A4). (Yield 65%).

式(1-23)所示化合物之結構係藉由元素分析而確定。分析機器係使用ICP發光分析裝置(ICPS-8100，島津製作所(股)製造)。The structure of the compound represented by the formula (1-23) is determined by elemental analysis. The analysis machine was an ICP luminescence analyzer (ICPS-8100, manufactured by Shimadzu Corporation).

(實施例7)(Example 7)

除了將染料A1換成染料A3以外，與實施例1同樣地獲得著色感光性樹脂組合物7。與實施例1同樣地對著色感光性樹脂組合物7進行評價，結果所得著色塗膜之xy色度座標(Rx，Ry)(色度)為(0.641，0.326)，亮度RY為20.3。又，耐溶劑試驗中，浸漬前後之色差ΔEab＊為0.7而良好。The colored photosensitive resin composition 7 was obtained in the same manner as in Example 1 except that the dye A1 was changed to the dye A3. The colored photosensitive resin composition 7 was evaluated in the same manner as in Example 1. As a result, the xy chromaticity coordinates (Rx, Ry) (chromaticity) of the obtained colored coating film were (0.641, 0.326), and the luminance RY was 20.3. Further, in the solvent resistance test, the color difference ΔEab* before and after the immersion was 0.7 and was good.

使用實施例1、2及4~7之著色感光性樹脂組合物而形成之著色塗膜可確認到良好之耐溶劑性。由此可知，可獲得表現出良好之耐溶劑性之著色圖案及高品質之彩色濾光片。The coloring coating film formed using the colored photosensitive resin compositions of Examples 1, 2, and 4 to 7 was confirmed to have good solvent resistance. From this, it is understood that a color pattern exhibiting good solvent resistance and a high-quality color filter can be obtained.

[產業上之可利用性][Industrial availability]

本發明之著色感光性樹脂組合物可形成耐溶劑性良好之著色塗膜、著色圖案及高品質之彩色濾光片。The colored photosensitive resin composition of the present invention can form a color coating film having a good solvent resistance, a colored pattern, and a high-quality color filter.

Claims (9)

一種著色感光性樹脂組合物，其含有著色劑、樹脂、光聚合性化合物、光聚合起始劑及溶劑，且著色劑為包含式(1)所示化合物者， [式(1)中，R1 ~R18 彼此獨立表示氫原子、鹵素原子、碳數1~8之1價脂肪族烴基、硝基、-SO2 R29 或-SO2 R32 ；R29 表示-OH或-NHR30 ；R30 表示氫原子、碳數1~8之1價脂肪族烴基、可經碳數1~4之烷基取代之環己基、-R31 -O-R32 、-R31 -CO-O-R32 、-R31 -O-CO-R32 、或碳數7~10之芳烷基；R31 表示碳數1~8之2價脂肪族烴基；R32 表示碳數1~8之1價脂肪族烴基；R19 及R20 彼此獨立表示氫原子、甲基、乙基或胺基；M1 表示Cr或Co；R21 ~R24 彼此獨立表示氫原子、碳數1~8之1價脂肪族烴基或碳數6~10之1價芳香族烴基，該脂肪族烴基及該芳香族烴基所含之氫原子可經羥基、-OR32 、磺基、-SO3 Na、-SO3 K或鹵素原子取代；R25 及R26 分別獨立表示氫原子或甲基；R27 表示伸乙基、丙烷-1,3-二基或丙烷-1,2-二基；R28 表示氫原子或碳數1~4之烷基；n表示1~4之整數；於n為2以上之整數時，複數個R27 可彼此相同亦可不同]。A colored photosensitive resin composition containing a colorant, a resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and the colorant is a compound containing the compound of the formula (1). [In the formula (1), R 1 to R 18 each independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, -SO 2 R 29 or -SO 2 R 32 ; R 29 Represents -OH or -NHR 30 ; R 30 represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, -R 31 -OR 32 , -R 31- CO-OR 32 , -R 31 -O-CO-R 32 , or an aralkyl group having 7 to 10 carbon atoms; R 31 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms; and R 32 represents a carbon number of 1 a monovalent aliphatic hydrocarbon group of ~8; R 19 and R 20 independently represent a hydrogen atom, a methyl group, an ethyl group or an amine group; M 1 represents Cr or Co; and R 21 to R 24 independently represent a hydrogen atom and a carbon number of 1; a monovalent aliphatic hydrocarbon group of -8 or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the aliphatic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may pass through a hydroxyl group, -OR 32 , a sulfo group, -SO 3 Na , -SO 3 K or a halogen atom; R 25 and R 26 each independently represent a hydrogen atom or a methyl group; R 27 represents an exoethyl group, a propane-1,3-diyl group or a propane-1,2-diyl group; 28 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms of; n represents an integer of 1 to 4; when n is an integer of at least 2, the plural R 27 may be identical to each other It may be different]. 如請求項1之著色感光性組合物，其中著色劑係進而包含顏料者。The colored photosensitive composition of claim 1, wherein the colorant further comprises a pigment. 如請求項2之著色感光性樹脂組合物，其中顏料為選自由C.I.顏料黃138、C.I.顏料黃139、C.I.顏料黃150、C.I.顏料紅177、C.I.顏料紅242及C.I.顏料紅254所組成之群中之至少一種。The colored photosensitive resin composition of claim 2, wherein the pigment is selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Red 177, CI Pigment Red 242, and CI Pigment Red 254. At least one of them. 如請求項1或2之著色感光性樹脂組合物，其中樹脂為含有以下共聚物之樹脂，該共聚物具有來源於具有碳數2~4之環狀醚及乙烯性不飽和雙鍵的單體之結構單元、以及來源於選自由不飽和羧酸及不飽和羧酸酐所組成之群中的至少一種之結構單元。The colored photosensitive resin composition according to claim 1 or 2, wherein the resin is a resin containing a copolymer having a monomer derived from a cyclic ether having 2 to 4 carbon atoms and an ethylenically unsaturated double bond. The structural unit and the structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. 一種著色圖案，其係使用如請求項1或2之著色感光性樹脂組合物而形成。A colored pattern formed by using the colored photosensitive resin composition of claim 1 or 2. 一種彩色濾光片，其含有如請求項5之著色圖案。A color filter containing a colored pattern as claimed in claim 5. 一種以式(2)所示之化合物， [式(2)中，R1 ~R18 彼此獨立表示氫原子、鹵素原子、碳數1~8之1價脂肪族烴基、硝基、-SO2 R29 或-SO2 R32 ；R29 表示-OH或-NHR30 ；R30 表示氫原子、碳數1~8之1價脂肪族烴基、可經碳數1~4之烷基取代之環己基、-R31 -O-R32 、-R31 -CO-O-R32 、-R31 -O-CO-R32 、或碳數7~10之芳烷基；R31 表示碳數1~8之2價脂肪族烴基；R32 表示碳數1~8之1價脂肪族烴基；R19 及R20 彼此獨立表示氫原子、甲基、乙基或胺基；M1 表示Cr或Co；R21 ~R24 彼此獨立表示氫原子、碳數1~8之1價脂肪族烴基或碳數6~10之1價芳香族烴基，該脂肪族烴基及該芳香族烴基所含之氫原子可經羥基、-OR32 、磺基、-SO3 Na、-SO3 K或鹵素原子取代；R25 及R26 分別獨立表示氫原子或甲基]。a compound represented by formula (2), [In the formula (2), R 1 to R 18 each independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, -SO 2 R 29 or -SO 2 R 32 ; R 29 ; Represents -OH or -NHR 30 ; R 30 represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, -R 31 -OR 32 , -R 31- CO-OR 32 , -R 31 -O-CO-R 32 , or an aralkyl group having 7 to 10 carbon atoms; R 31 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms; and R 32 represents a carbon number of 1 a monovalent aliphatic hydrocarbon group of ~8; R 19 and R 20 independently represent a hydrogen atom, a methyl group, an ethyl group or an amine group; M 1 represents Cr or Co; and R 21 to R 24 independently represent a hydrogen atom and a carbon number of 1; a monovalent aliphatic hydrocarbon group of -8 or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the aliphatic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may pass through a hydroxyl group, -OR 32 , a sulfo group, -SO 3 Na , -SO 3 K or a halogen atom; R 25 and R 26 each independently represent a hydrogen atom or a methyl group]. 如請求項7之化合物，其中M1 為Cr。The compound of claim 7, wherein M 1 is Cr. 如請求項7或8之化合物，其中R1 ~R18 中至少一個為硝基。The compound of claim 7 or 8, wherein at least one of R 1 to R 18 is a nitro group.
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