WO2020226099A1 - Colored curable resin composition - Google Patents

Colored curable resin composition Download PDF

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Publication number
WO2020226099A1
WO2020226099A1 PCT/JP2020/018102 JP2020018102W WO2020226099A1 WO 2020226099 A1 WO2020226099 A1 WO 2020226099A1 JP 2020018102 W JP2020018102 W JP 2020018102W WO 2020226099 A1 WO2020226099 A1 WO 2020226099A1
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group
carbon atoms
substituent
compound
formula
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PCT/JP2020/018102
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French (fr)
Japanese (ja)
Inventor
岡本　信之
紘也 竹田
佳亮 井上
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住友化学株式会社
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Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to KR1020217039460A priority Critical patent/KR20220007628A/en
Priority to CN202080033908.6A priority patent/CN113795521B/en
Publication of WO2020226099A1 publication Critical patent/WO2020226099A1/en

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F275/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers containing phosphorus, selenium, tellurium or a metal as defined in group C08F30/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

Definitions

  • the present invention relates to a colored curable resin composition.
  • Patent Document 1 describes a solvent, a reactive diluent, a photopolymerization initiator, a colorant, and the formula (1):
  • Examples of the method for forming the color filter from the color curable resin composition include a photolithography method and a method using an inkjet device.
  • a color curable resin composition is usually applied onto a substrate, and volatile components such as a solvent are removed by heat drying (prebaking) and / or vacuum drying to form a composition layer, and the composition is formed. It includes a step of irradiating (exposing) light on the layer and bringing a developing solution into contact with the exposed composition layer to form (develop) a colored pattern or a colored coating film. After this development, post-baking is often performed to heat the coloring pattern.
  • the thickness of the colored pattern or the colored coating film may be significantly reduced by post-baking.
  • the present invention has been made in view of such circumstances, and an object of the present invention is a coloring curable resin composition capable of suppressing a decrease in a coloring pattern or a thickness of a coloring coating film due to heating (particularly post-baking). Is to provide.
  • a color curable resin composition containing a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).
  • the color curable resin composition further contains a phenolic antioxidant (E).
  • the resin (B) is the formula (1b):
  • R 1B represents a hydrogen atom or a methyl group.
  • R 2B to R 4B independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
  • n represents an integer from 1 to 10, and * represents the bond position. However, at least one of R 2B to R 4B is an alkoxy group having 1 to 6 carbon atoms.
  • the resin (B1) contains a structural unit (b1-1), a structural unit (b1-2) derived from a polymerizable unsaturated compound having an acidic group, and another structural unit (b1-3).
  • Color curable resin composition [8] The colorant (A) has the formula (A3-1):
  • R 41a and R 42a each independently have a hydrogen atom and a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and a substituent. It represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R 41a and R 42a are bonded to each other.
  • It represents an aromatic hydrocarbon group, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or 3 to 10 members together with a nitrogen atom to which R 43a and R 44a are bonded and bonded to each other.
  • Forming a nitrogen-containing heterocycle of R 47a ⁇ R 54a are each independently a hydrogen atom, a halogen atom, a nitro group, hydroxy group, -SO 3 -, -SO 2 -N - have -SO 2 -R f or a substituent,
  • R f represents a fluoroalkyl group having 1 to 12 carbon atoms.
  • Ring T 1a represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms which may have a substituent or a 5 to 10 member aromatic heterocycle which may have a substituent.
  • the substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
  • aromatic hydrocarbon group substituents which may be possessed by the carbon number of 6 to 14, a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - -SO 2 - R f , and at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have a substituent.
  • Substituents which may be the aralkyl group have the carbon number of 7 to 30, a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - -SO 2 -R f, And at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have substituents.
  • Aromatic hydrocarbon ring substituent that have the carbon number of 6 to 14, a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - -SO 2 - R f , and at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have a substituent.
  • said 5 to 10-membered aromatic heterocyclic ring substituent which may have of a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - -SO 2 -R f , And at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have substituents.
  • the substituent which the alkyl group having 1 to 8 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
  • r represents an integer of 1 or more Mr + represents a hydrogen ion, an r-valent metal ion or N + (R 55a ) 4 , and the four R 55a may be the same or different.
  • R 55a represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.
  • k is the formula (A3-1a):
  • R 41b and R 42b each independently have a hydrogen atom and a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent which may have a substituent. May have 6 to carbon atoms Represents an aromatic hydrocarbon group of 14 or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R 41b and R 42b are bonded and 3 together with the nitrogen atom to which they are bonded.
  • Forming a nitrogen-containing heterocycle of ⁇ 10 members, R 43b and R 44b independently have a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and 6 to 14 carbon atoms which may have a substituent.
  • It represents an aromatic hydrocarbon group, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or 3 to 10 members together with a nitrogen atom to which R 43b and R 44b are bonded and bonded to each other.
  • Forming a nitrogen-containing heterocycle of R 47b to R 54b each independently represent an alkyl group having 1 to 8 carbon atoms which may have a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or a substituent.
  • Ring T 1b represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms which may have a substituent or a 5 to 10 member aromatic heterocycle which may have a substituent.
  • the substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
  • the substituents that the aromatic hydrocarbon group having 6 to 14 carbon atoms may have may have a halogen atom, a nitro group, a hydroxy group, a formyl group, and a substituent having 1 to 8 carbon atoms.
  • At least one selected from the group consisting of alkyl groups of The substituents that the aralkyl group having 7 to 30 carbon atoms may have are a halogen atom, a nitro group, a hydroxy group, a formyl group, and an alkyl group having 1 to 8 carbon atoms that may have a substituent.
  • At least one selected from the group consisting of The substituents that the aromatic hydrocarbon ring having 6 to 14 carbon atoms may have may have a halogen atom, a nitro group, a hydroxy group, a formyl group, and a substituent having 1 to 8 carbon atoms.
  • At least one selected from the group consisting of alkyl groups of Substituents that the 5- to 10-membered aromatic heterocycle may have are halogen atoms, nitro groups, hydroxy groups, formyl groups, and alkyl having 1 to 8 carbon atoms that may have substituents.
  • At least one selected from the group of groups, The substituent which the alkyl group having 1 to 8 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
  • the saturated hydrocarbon group having 1 to 20 carbon atoms is a saturated hydrocarbon group having 2 to 20 carbon atoms
  • -CH 2- contained in the saturated hydrocarbon group is replaced with -O- or -CO-.
  • the alkyl group having 1 to 8 carbon atoms is an alkyl group having 2 to 8 carbon atoms
  • -CH 2- contained in the alkyl group may be replaced with -O- or -CO-.
  • m represents an integer of 1 or more [Y] m- represents an m-valent anion, and when m is an integer of 2 or more, the formula (A3-2c):
  • rings T 1b , R 41b to R 44b and R 47b to R 54b are synonymous with the above, respectively.
  • the plurality of cations represented by may be the same or different.
  • the colored curable resin composition of the present invention it is possible to suppress a decrease in the thickness of the colored pattern or the colored coating film due to heating (particularly post-baking).
  • the color curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a phenolic antioxidant (E). Further, the resin (B) includes a resin (B1) containing a structural unit (b1-1) represented by the above formula (1b).
  • a colorant (A) a colorant (A)
  • a resin (B) a polymerizable compound (C)
  • D polymerization initiator
  • E a phenolic antioxidant
  • the resin (B) includes a resin (B1) containing a structural unit (b1-1) represented by the above formula (1b).
  • each component and the raw material for producing each component described in the present specification may be used, or two or more types may be used in combination.
  • the colorant (A) is classified into a solvent-soluble dye (A1) and a solvent-insoluble pigment (A2).
  • the colorant (A) comprises both the dye (A1) and the pigment (A2).
  • the dye (A1) preferably contains at least one dye selected from the group consisting of xanthene dyes, triarylmethane dyes and coumarin dyes.
  • the total amount thereof is preferably 1% by weight or more, 100% by weight or less, and more preferably 2% by weight or more, based on the entire dye (A1). It is 100% by weight or less, more preferably 5% by weight or more and 100% by weight or less.
  • the dye (A1) more preferably contains a xanthene dye.
  • a xanthene dye When a xanthene dye is used, its content is preferably 1% by weight or more and 100% by weight or less, more preferably 2% by weight or more and 100% by weight or less, based on the entire dye (A1). More preferably, it is 5% by weight or more, 100% by weight or less, and most preferably 100% by weight. That is, the dye (A1) is most preferably composed of a xanthene dye.
  • the xanthene dye is a dye containing a compound having a xanthene skeleton in the molecule.
  • examples of the xanthene dye include C.I. I. Acid Red 51 (hereinafter, the description of CI Acid Red is omitted and only the number is described. The same applies to the others), 52, 87, 92, 94, 289, 388, C.I. I. Acid Violet 9, 30, 102, C.I. I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. I. Basic Red 10, 11, C.I. I. Basic Violet 10 (Rhodamine B), 11, C.I. I. Solvent Red 218, C.I. I. Modant Red 27, C.I. I.
  • Examples thereof include reactive red 36 (rose bengal B), sulforhodamine G, xanthene dyes described in JP-A-2010-32999, and xanthene dyes described in Japanese Patent No. 4492760.
  • the xanthene dye is preferably one that dissolves in an organic solvent.
  • Preferred xanthene dyes include compounds represented by the formula (1a) (hereinafter sometimes referred to as "compound (1a)").
  • Compound (1a) may be a tautomer thereof.
  • its content is preferably 50% by weight or more, more preferably 70% by weight or more, still more preferably 90% by weight or more, based on the total amount of the xanthene dye.
  • R 1 to R 4 each independently have a hydrogen atom and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and a substituent.
  • the stands, the -CH 2 - contained in the saturated hydrocarbon group - is, -O -, - CO- or -NR 11 - may be replaced by, R 1 and R 2 may be combined to form a ring containing a nitrogen atom, and R 3 and R 4 may be combined to form a ring containing a nitrogen atom.
  • R 5 is, -OH, -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO Represents 2 NR 9 R 10
  • R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • m represents an integer from 0 to 5, and when m is 2 or more, a plurality of R 5s may be the same or different.
  • a represents an integer of 0 or 1 and represents X represents a halogen atom Z + stands for N + (R 11 ) 4 , Na + or K + , and the four R 11s may be the same or different.
  • R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom.
  • R 9 and R 10 each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a substituent, and are contained in the saturated aliphatic hydrocarbon group.
  • CH 2 - is, -O -, - CO -, - NH- or -NR 8 - may have I placed conversion in, R 9 and R 10, 3-10 membered containing nitrogen atoms bonded to each other It may form a heterocycle of rings, R 11 represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.
  • R 12 represents an alkanediyl group having 1 to 10 carbon atoms
  • -CH 2 contained in the alkanediyl group - is, -O -, - CO -, - NR 8 -, - OCO -, - COO-, -OCONH -, - CONH- or -NHCO-
  • R 13 represents a hydrogen atom, a hydroxy group, an alkyl group or an alkoxy group having 1 to 4 carbon atoms having 1 to 4 carbon atoms,
  • the plurality of R 13s may be the same or different, respectively.
  • Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent in R 1 to R 4 include a phenyl group, a tolyl group, a xsilyl group, a mesityl group, a propylphenyl group and the like. Examples include a butylphenyl group.
  • the aromatic hydrocarbon group substituent which may have a halogen atom, -R 8, -OH, -OR 8 , -SO 3 -, -SO 3 H, -SO 3 - Z +, - Examples thereof include CO 2 H, -CO 2 R 8 , -SR 8 , -SO 2 R 8 , -SO 3 R 8 or -SO 2 NR 9 R 10 .
  • -SO 3 -, -SO 3 H , -SO 3 - Z + and -SO 2 NR 9 R 10 is preferably, -SO 3 - Z + and -SO 2 NR 9 R 10 is more preferred.
  • -SO 3 - Z + -SO 3 - N + (R 11 ) 4 is preferable.
  • the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 1 to R 4 and R 8 to R 11 may be linear, branched chain or cyclic. Examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, icosyl group, isopropyl group, isobutyl group, Alkyl group having 1 to 20 carbon atoms such as isopentyl group, neopentyl group and 2-ethylhexyl group; 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group.
  • the alicyclic saturated hydrocarbon group of
  • Substituents that the saturated hydrocarbon groups in R 1 to R 4 may have include, for example, aromatic hydrocarbon groups having 6 to 10 carbon atoms, halogen atoms and carboxy groups. Substituents that the saturated hydrocarbon groups in R 9 and R 10 may have include, for example, hydroxy groups and halogen atoms.
  • Examples of the ring formed by R 1 and R 2 together and the ring formed by R 3 and R 4 together include the following.
  • Examples of -OR 8 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group and an icosyloxy group.
  • Examples of -CO 2 R 8 include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, an icosyloxycarbonyl group and the like.
  • Examples of the -SR 8 include a methylsulfanil group, an ethylsulfanil group, a butylsulfanil group, a hexylsulfanil group, a decylsulfanil group, an icosylsulfanil group and the like.
  • -SO 2 R 8 includes, for example, a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, an icosylsulfonyl group and the like.
  • Examples of the -SO 3 R 8 include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group and an icosyloxysulfonyl group.
  • R 10 includes, for example: Sulfamoyl group; N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-Butyl sulfamoyl group, N-tert-Butyl sulfamoyl group, N-pentyl sulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methyl) sulfam
  • R 5 is preferably -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 -, -SO 3 - Z +, a -SO 3 H or SO 2 NHR 9, more preferably is SO 3 -, -SO 3 - Z +, a -SO 3 H or SO 2 NHR 9.
  • m is preferably 1 to 4, more preferably 1 or 2.
  • Examples of the alkyl group having 1 to 6 carbon atoms in R 6 and R 7 include those having 1 to 6 carbon atoms among the alkyl groups listed above.
  • Examples of the aralkyl group having 7 to 10 carbon atoms in R 11 include a benzyl group, a phenylethyl group, a phenylbutyl group and the like.
  • Examples thereof include a group, an isopentylene group, an isohexylene group, an isooctylene group, a 2-ethylhexylene group and the like.
  • an alkanediyl group having 1 to 6 carbon atoms is preferable, and an alkanediyl group having 1 to 4 carbon atoms is more preferable.
  • Examples of the alkyl group having 1 to 4 carbon atoms in R 13 include a methyl group, an ethyl group, a propyl group and a butyl group.
  • Examples of the alkoxy group having 1 to 4 carbon atoms in R 13 include a methoxy group, an ethoxy group, a propoxy group, a t-butoxy group and the like.
  • the R 13, a methyl group, an ethyl group, a methoxy group, an ethoxy group are preferred, a methoxy group or an ethoxy group is more preferable.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • Z + is N + (R 11 ) 4 , Na + or K + , preferably N + (R 11 ) 4 .
  • N + (R 11) 4 of the four R 11, at least those two is a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms are preferred. It is preferable that the total number of carbon atoms of the four R 11 is 20 to 80, and more preferably 20 to 60.
  • N + (R 11 ) 4 is present in the compound (1a), if R 11 is these groups, the color filter containing the compound (1a) and having less foreign matter can be obtained from the color curable resin composition of the present invention. Can be formed.
  • compound (2a) a compound represented by the formula (2a) (hereinafter, may be referred to as “compound (2a)”) is preferable.
  • Compound (2a) may be a tautomer thereof.
  • R 21 to R 24 each independently have a hydrogen atom and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent which may have a carboxy group.
  • R 21 and R 22 may be combined to form a ring containing a nitrogen atom
  • R 23 and R 24 may be combined to form a ring containing a nitrogen atom.
  • R 25 is, -SO 3 - represents Z1 + or -SO 2 NHR 26, -, -SO 3 H, -SO 3 m represents an integer from 0 to 5, and when m is 2 or more, a plurality of R 25s may be the same or different.
  • a represents an integer of 0 or 1 and represents X represents a halogen atom
  • R 26 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
  • Z1 + represents N + (R 27 ) 4 , Na + or K +
  • the four R 27s may be the same or different, and R 27 is a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
  • R 27 is a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
  • Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R 21 to R 24 include the same groups as those mentioned as the aromatic hydrocarbon group of R 1 to R 4 described above.
  • the aromatic hydrocarbon group substituents which may be possessed by, for example, -SO 3 -, -SO 3 H , -SO 3 - Z1 +, -SO 3 R 26 or -SO 2 NHR 26 can be mentioned Be done.
  • the description of the group represented by * -R 12- Si (R 13 ) 3 in R 21 to R 24 is the same as above.
  • R 21 to R 24 As a combination of R 21 to R 24 , R 21 and R 23 are hydrogen atoms, R 22 and R 24 are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the aromatic hydrocarbons are said to be. groups, -SO 3 -, -SO 3 H , -SO 3 - Z1 +, what is preferably substituted by -SO 3 R 26 or -SO 2 NHR 26.
  • R 21 and R 23 are hydrogen atoms
  • R 22 and R 24 are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the aromatic hydrocarbon group is -SO. 3 - Z1 + or those which have been substituted with -SO 2 NHR 26.
  • R 21 to R 24 are these groups, a color filter having excellent heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (2a).
  • Examples of the ring containing a nitrogen atom formed by R 21 and R 22 together and the ring containing a nitrogen atom formed by R 23 and R 24 together include R 1 and R 2 together.
  • Examples of the aliphatic heterocycle include the following.
  • Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 21 to R 24 , R 26 and R 27 include the same groups as those mentioned as the saturated hydrocarbon group in R 8 to R 11 . Be done.
  • R 21 to R 24 are monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms which may have a carboxy group
  • R 21 to R 24 each independently have a carboxy group. It is preferably a methyl group, an ethyl group which may have a carboxy group, or a propyl group which may have a carboxy group.
  • R 26 in -SO 3 R 26 and -SO 2 NHR 26 preferably branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 6-12 carbon atoms, 2-Ethylhexyl groups are more preferred.
  • R 26 is these groups, a color filter containing less foreign matter can be formed from the colored curable resin composition of the present invention containing the compound (2a).
  • Z1 + is N + (R 27 ) 4 , Na + or K + , preferably N + (R 27 ) 4 .
  • N + (R 27) 4 of the four R 27, it is preferred that at least two is a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. The total number of carbon atoms in the four R 27 is preferably 20 to 80, more preferably from 20 to 60.
  • N + (R 27 ) 4 is present in the compound (2a), when R 27 is these groups, the color curable resin composition of the present invention containing the compound (2a) produces less foreign matter.
  • a color filter can be formed.
  • m is preferably 1 to 4, more preferably 1 or 2.
  • compound (3a) a compound represented by the formula (3a) (hereinafter, may be referred to as “compound (3a)”) is also preferable.
  • Compound (3a) may be a tautomer thereof.
  • R 31 and R 32 are independently monovalent saturated hydrocarbon groups having 1 to 10 carbon atoms, or groups represented by * -R 12- Si (R 13 ) 3 ( In the above formula, * represents the bond position with the nitrogen atom), and the saturated hydrocarbon group is substituted with a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, a halogen atom or a carboxy group.
  • R 33 and R 34 independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.
  • R 31 and R 33 may be combined to form a ring containing a nitrogen atom
  • R 32 and R 34 may be combined to form a ring containing a nitrogen atom
  • p and q is -O - - -CH 2 is good, contained in the saturated hydrocarbon group, - CO- or -NR 11 - it may be replaced by the aromatic hydrocarbon groups, having 1 to 3 carbon atoms It may be substituted with an alkoxy group
  • R 33 and R 34 independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.
  • R 31 and R 33 may be combined to form
  • Well, and R 11 are synonymous with the above. ]
  • the monovalent saturated hydrocarbons having 1 to 10 carbon atoms in R 31 and R 32 may be linear, branched or cyclic. Examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2
  • An alkyl group having 1 to 10 carbon atoms such as an ethylhexyl group
  • an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group can be mentioned.
  • R 31 and R 32 The description of the group represented by * -R 12- Si (R 13 ) 3 in R 31 and R 32 is the same as above.
  • Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms that R 31 and R 32 may have as a substituent include a phenyl group.
  • Examples of the alkyl group having 1 to 3 carbon atoms that the aromatic hydrocarbon group may have as a substituent include a methyl group, an ethyl group and a propyl group.
  • alkoxy group having 1 to 3 carbon atoms that the aromatic hydrocarbon group may have as a substituent include a methoxy group, an ethoxy group, a propoxy group and the like.
  • R 31 and R 32 are monovalent saturated hydrocarbon groups having 1 to 3 carbon atoms, which may independently have a carboxy group.
  • Examples of the alkyl group having 1 to 4 carbon atoms in R 33 and R 34 include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and the like. ..
  • Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R 33 and R 34 include a methyl sulfanyl group, an ethyl sulfanyl group, a propyl sulfanyl group, a butyl sulfanyl group and an isopropyl sulfanyl group.
  • Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R 33 and R 34 include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group and an isopropylsulfonyl group.
  • R 33 and R 34 are preferably alkyl groups having 1 to 4 carbon atoms, and more preferably methyl groups.
  • P and q are preferably integers of 0 to 2, and more preferably 0 or 1.
  • Examples of the compound (1a) include compounds represented by the formulas (1-1) to (1-45).
  • R 40 in the following formula represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group. ..
  • R 26 in the following formula represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms as described above.
  • Examples of the xanthene dye include C.I. I. Sulfonamides of Acid Red 289, C.I. I. Quaternary Ammonium Salt of Acid Red 289, C.I. I. Sulfonamides of Acid Violet 102 or C.I. I. A quaternary ammonium salt of Acid Violet 102 is preferred.
  • Examples of such a compound include compounds represented by formulas (1-1) to (1-8), formulas (1-11) or formulas (1-12). Further, a compound represented by any of the formulas (1-24) to (1-33), formula (1-44) and formula (1-45) is also preferable because of its excellent solubility in an organic solvent. ..
  • xanthene dye a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink R-H / C” manufactured by Chugai Pharmaceutical Co., Ltd. and “Rhodamin 6G” manufactured by Taoka Chemical Co., Ltd.) can be used. Further, it is also possible to synthesize using a commercially available xanthene dye as a starting material with reference to a known technique (for example, JP-A-2010-32999).
  • the triarylmethane dye is preferably of the formula (4a):
  • R 1A to R 8A independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or a saturated hydrocarbon group having 1 to 20 carbon atoms, and of the saturated hydrocarbon group. When the number of carbon atoms is 2 to 20, -CH 2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-.
  • Each of R 9A to R 12A independently has a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, and an aromatic hydrocarbon group or a substituent having 6 to 20 carbon atoms which may have a substituent.
  • It represents an aralkyl group having 7 to 30 carbon atoms which may be used, and the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or a halogen atom, and the saturated hydrocarbon group has a carbon number of 7 to 30.
  • -CH 2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-, and the nitrogen atom to which R 9A and R 10A are bonded to each other is bonded. They may form a ring with, or R 11A and R 12A may bond to form a ring with the nitrogen atom to which they bind.
  • R 13A represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted.
  • [G] g- represents a counter anion of arbitrary g valence, and g represents 0 or any natural number, and when g is a natural number of 2 or more, the plurality of cations in formula (4a) are They may be the same or different.
  • It is a compound represented by.
  • a coumarin dye is a dye containing a compound having a coumarin skeleton in the molecule.
  • the coumarin dye include C.I. I. Acid Yellow 227, 250; C.I. I. Disperse Yellow 82, 184; C.I. I. Solvent Orange 112; C.I. I. Solvent Yellow 160, 172; coumarin dyes and the like described in Japanese Patent No. 12999948. Those that dissolve in an organic solvent are preferable.
  • dyes other than the above include dyes listed in the Color Index (The Society of Dyers and Colorists Publishing) and dyes listed in the Dyeing Note (Color Dyeing Company).
  • the dye include azo dye, cyanine dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acrydin dye, styryl dye, quinoline dye and nitro dye. .. Of these, dyes that dissolve in organic solvents are preferred.
  • the dye include the following. (1) C.I. I. Solvent dye C. I. Solvent Yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; C. I. Solvent Orange 2,7,11,15,26,41,54,56,99; C. I. Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247; C. I.
  • C.I. I. Direct dye C. I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141; C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; C. I. Direct blue 40; etc.
  • C.I. I. Mordant dye C. I. Modant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; C. I. Modant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; etc.
  • pigment (A2) a known pigment can be used without particular limitation, and examples thereof include pigments described in the Color Index (The Society of Dyers and Colorists Publishing).
  • Examples of the pigment (A2) include the following: C. I. Pigment Yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,129,137,138, Yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; C. I.
  • the pigment (A2) is preferably a red pigment or a blue pigment.
  • the red pigment preferably has absorption in a wavelength region of 580 nm or less, and more preferably has absorption in a wavelength region of 480 nm or more and 560 nm or less. Further, the red pigment preferably transmits light in a wavelength range of 610 nm or more.
  • red pigment a known pigment can be used, and examples thereof include those described in the Color Index (The Society of Dyers and Colorists Publishing).
  • red pigments anthraquinone pigments, azo pigments, quinacridone pigments, perylene pigments and diketopyrrolopyrrole pigments are preferable, and anthraquinone pigments and diketopyrrolopyrrole pigments are more preferable.
  • preferable red pigments include C.I. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 202, 208, 209, 215, 216, 224, 242, 254, 255, 264, Examples thereof include compounds represented by the formula (P) described in 265, 266, 268, 269, 273, and Japanese Patent Application Laid-Open No. 2013-014750. Among these, C.I. I. Pigment Red 177, 208, 242, 254, 269, and the compound represented by the formula (P) described in JP2013-014750 are more preferable, and C.I. I. Pigment Red 177, 254, and the compound represented by the formula (P) described in JP2013-014750 are more preferable.
  • the blue pigment preferably has absorption in the wavelength range of 700 nm or less, and more preferably has absorption in the wavelength range of 580 nm or more and 650 nm or less. Further, the blue pigment preferably transmits light in a wavelength range of 400 nm or more.
  • the blue pigment is preferably a phthalocyanine pigment, more preferably a copper phthalocyanine pigment and / or a zinc phthalocyanine pigment, still more preferably a copper halide phthalocyanine pigment and / or a halogenated zinc phthalocyanine pigment, and particularly preferably a copper halide. It is a phthalocyanine pigment.
  • C.I. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 are preferred.
  • I. Pigment Blue 15, 15: 3, 15: 4, 15: 6 are more preferred,
  • C.I. I. Pigment Blue 15: 6 is particularly preferred.
  • the pigment is treated with a rosin, a surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, a graft treatment on the pigment surface with a polymer compound or the like, and atomization by a sulfuric acid atomization method or the like.
  • Treatment, cleaning treatment with an organic solvent, water, etc. for removing impurities, removal treatment of ionic impurities by an ion exchange method, or the like may be performed.
  • the pigment preferably has a uniform particle size.
  • the dispersant examples include a surfactant.
  • the surfactant may be any of a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant.
  • examples of the surfactant include polyester-based surfactants, polyamine-based surfactants, acrylic-based surfactants, and the like.
  • Commercially available dispersants include, for example, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoei Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca), EFKA (manufactured by BASF), and Ajispar (registered trademark). (Ajinomoto Fine Techno Co., Ltd.), DISPERBYK (registered trademark) (Big Chemie Co., Ltd.), BYKLPN (manufactured by BYK Co., Ltd.) and the like.
  • the content thereof is preferably 1 part by weight or more and 500 parts by weight or less, and more preferably 5 parts by weight or more and 300 parts by weight with respect to 100 parts by weight of the pigment (A2). It is as follows. When the content of the dispersant is within the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.
  • the content of the colorant (A) is preferably 1% by weight or more and 60% by weight or less, more preferably 3% by weight or more and 55% by weight or less, still more preferably, with respect to the total amount of solid content. It is 5% by weight or more and 50% by weight or less.
  • the "total amount of solid content" in the present specification means an amount obtained by subtracting the content of the solvent from the total amount of the colored curable resin composition.
  • a color filter having a sufficient color density can be obtained.
  • a required amount of the resin or the polymerizable compound can be contained in the composition, so that a color filter having sufficient mechanical strength can be formed. Can be done.
  • the total amount of solids and the content of each component relative to the total amount can be measured by a known analytical means such as liquid chromatography or gas chromatography.
  • the dye (A1) When the dye (A1) is used, its content is preferably 0.5% by weight or more, more preferably 1% by weight or more, and 60% by weight or less, based on the total amount of solids. It is more preferable that the content is 55% by weight or less. When the content of the dye (A1) is within the above range, a colored curable resin composition having good developability with respect to an alkaline developer can be obtained.
  • the pigment (A2) When the pigment (A2) is used, its content is preferably 1% by weight or more, more preferably 1.5% by weight or more, and 60% by weight or less, based on the total amount of solids. It is preferably 55% by weight or less, and further preferably 50% by weight or less. When the content of the pigment (A2) is within the above range, a color filter having a good chromaticity can be obtained.
  • the weight ratio of the dye (A1) to the pigment (A2) is preferably 1:99 to 99: 1. Yes, more preferably 1:99 to 95: 5, and particularly preferably 5:95 to 90:10.
  • the colorant (A) is of formula (A3-1) :.
  • compound (A3-2) It contains at least one compound (A3) selected from the group consisting of the compound represented by (hereinafter, may be referred to as “compound (A3-2)").
  • Compound (A3) (ie, compound (A3-1) and compound (A3-2)) depends on its structure (eg, the type of counterion (Mr + ) k-1 and [Y] m- ). It becomes a "solvent-soluble dye” or a "solvent-insoluble pigment”. That is, the range of the compound (A3) includes both the compound which is a dye and the compound which is a pigment.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the saturated hydrocarbon group may be linear, branched or cyclic.
  • Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group and a hexadecyl group.
  • Icosyl group isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group and other alkyl groups with 1 to 20 carbon atoms; cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, tri Examples thereof include an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclodecyl group.
  • the alkyl group may be either linear or branched.
  • Examples of the alkyl group having 1 to 10 carbon atoms include those having 1 to 10 carbon atoms in the above-mentioned examples of the alkyl group having 1 to 20 carbon atoms.
  • examples of saturated hydrocarbon groups having 2 to 20 carbon atoms include those having 2 to 20 carbon atoms in the above-mentioned examples of saturated hydrocarbon groups having 1 to 20 carbon atoms.
  • the alkanediyl group may be either linear or branched.
  • the arcandyl group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an isopropylene group, an isobutylene group, a 2-methyltrimethylene group and an isopentylene.
  • Examples thereof include a group, an isohexylene group, an isooctylene group and a 2-ethylhexylene group.
  • the fluoroalkyl group may be either linear or branched.
  • Examples of the fluoroalkyl group having 1 to 12 carbon atoms include a monofluoromethyl group, a difluoromethyl group, a perfluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, and a perfluoroethyl group.
  • the alkoxy group may be either linear or branched.
  • Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an isopropoxy group, an isobutoxy group, an isopentyloxy group and a neopentyloxy group. Can be mentioned.
  • Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, and a 9-anthryl group.
  • Examples of the aralkyl group having 7 to 30 carbon atoms include a benzyl group, a phenethyl group, a naphthylmethyl group, and a 3-phenylpropyl group.
  • the nitrogen-containing heterocycle may be either a monocyclic ring or a condensed ring.
  • Examples of the 3- to 10-membered nitrogen-containing heterocycle include a pyrrolidine ring, a morpholine ring, a piperidine ring, and a piperazine ring.
  • the aromatic hydrocarbon ring may be either a monocyclic ring or a condensed ring.
  • the aromatic hydrocarbon ring having 6 to 14 carbon atoms may be any of a benzene ring, a naphthalene ring, a phenanthrene ring and an anthracene ring.
  • the aromatic heterocycle may be either a monocyclic ring or a condensed ring.
  • Examples of the 5- to 10-membered aromatic heterocycle include a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, a thiazole ring, a furan ring, a thiophene ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, and an indole ring.
  • Examples thereof include a benzimidazole ring, a benzothiazole ring, a quinoline ring, and a benzofuran ring.
  • R 41a and R 42a in the formula (A3-1) each independently have a hydrogen atom and a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and a substituent. It represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R 41a and R 42a are bonded to each other. It forms a 3- to 10-membered nitrogen-containing heterocycle with the bonding nitrogen atom.
  • the substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (A3-1) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group. is there.
  • the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (A3-1) is a saturated hydrocarbon group having 2 to 20 carbon atoms
  • -CH 2- contained in the saturated hydrocarbon group is -O-.
  • it may be replaced with -CO-.
  • -CH 2- does not include -CH 2 -bonded to a nitrogen atom and -CH 2- in the methyl group at the end of the saturated hydrocarbon group.
  • -CH 2- CH 2- contained in the saturated hydrocarbon group is not replaced with -O-O- or -CO-CO-.
  • Aromatic hydrocarbon group substituents which may be possessed by the carbon number of 6 to 14 in the formula (A3-1) is a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - it is at least one selected from the group consisting of an alkyl group of -SO 2 -R f, and substituents to 1 carbon atoms which may have a 8.
  • Substituents which may have an aralkyl group having 7 to 30 carbon atoms in the formula (A3-1) is a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - -SO 2- R f , and at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have substituents.
  • R f in the formula (A3-1) represents a fluoroalkyl group having 1 to 12 carbon atoms.
  • the substituent that the alkyl group having 1 to 8 carbon atoms in the formula (A3-1) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
  • alkyl group having 1 to 8 carbon atoms in the formula (A3-1) is an alkyl group having 2 to 8 carbon atoms
  • -CH 2- contained in the alkyl group is replaced with -O- or -CO-. May be.
  • the -CH 2 - The, -CH 2 in a methyl group is the terminal of the alkyl group - is not included.
  • -CH 2- CH 2- contained in the alkyl group is not replaced with -OO- or -CO-CO-.
  • R 41a is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms.
  • R 42a is preferably an alkyl group and -SO 3 having 1 to 8 carbon atoms - one as at least one substituent a phenyl group which may have a, more preferably substituent selected from the group consisting or 2 It has a number of alkyl group having 1 to 8 carbon atoms, and -SO 3 - a phenyl group optionally having a, more preferably one or two alkyl groups having 1 to 4 carbon atoms as a substituent a, and -SO 3 - is a phenyl group which may have a.
  • R 43a and R 44a in the formula (A3-1) each independently have a hydrogen atom and a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and a substituent. It represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R 43a and R 44a are bonded to each other. It forms a 3- to 10-membered nitrogen-containing heterocycle with the nitrogen atom.
  • R 43a is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms.
  • R 44a is preferably an alkyl group and -SO 3 having 1 to 8 carbon atoms - one as at least one substituent a phenyl group which may have a, more preferably substituent selected from the group consisting or 2 It has a number of alkyl group having 1 to 8 carbon atoms, and -SO 3 - a phenyl group optionally having a, more preferably one or two alkyl groups having 1 to 4 carbon atoms as a substituent a, and -SO 3 - is a phenyl group which may have a.
  • R 47a ⁇ R 54a in formula (A3-1) are each independently a hydrogen atom, a halogen atom, a nitro group, hydroxy group, -SO 3 -, -SO 2 -N - -SO 2 -R f, Alternatively, it represents an alkyl group having 1 to 8 carbon atoms which may have a substituent.
  • R 47a ⁇ R 54a are each independently preferably a hydrogen atom, an alkyl group or -SO 3 having 1 to 8 carbon atoms - a -, more preferably a hydrogen atom or -SO 3.
  • the ring T 1a in the formula (A3-1) may have a substituent and may have an aromatic hydrocarbon ring having 6 to 14 carbon atoms or a 5 to 10-membered aromatic which may have a substituent. Represents a heterocycle.
  • Aromatic hydrocarbon ring substituent which may be possessed by the carbon number of 6 to 14 in the formula (A3-1) is a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - it is at least one selected from the group consisting of an alkyl group of -SO 2 -R f, and substituents to 1 carbon atoms which may have a 8.
  • 5-10 membered aromatic heterocyclic ring substituent which may have a in the formula (A3-1) is a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N It is at least one selected from the group consisting of --SO 2- R f , and an alkyl group having 1 to 8 carbon atoms which may have a substituent.
  • Ring T 1a is preferably of formula (1t):
  • R 45a and R 46a in the formula (1t) may independently have a hydrogen atom and a substituent, and may have a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent. It represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R 45a and R 46a are bonded to each other. It forms a 3- to 10-membered nitrogen-containing heterocycle with a nitrogen atom.
  • the substituent that the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (1t) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
  • Aromatic hydrocarbon group substituents which may be possessed by the carbon number of 6 to 14 in the formula (1t) is a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N It is at least one selected from the group consisting of --SO 2- R f , and an alkyl group having 1 to 8 carbon atoms which may have a substituent.
  • Substituents which may have an aralkyl group having 7 to 30 carbon atoms in the formula (1t) is a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - -SO It is at least one selected from the group consisting of 2- R f , and an alkyl group having 1 to 8 carbon atoms which may have a substituent.
  • the substituent that the alkyl group having 1 to 8 carbon atoms in the formula (1t) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
  • R 45a is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms.
  • R 46a is preferably an alkyl group and -SO 3 having 1 to 8 carbon atoms - one as at least one substituent a phenyl group which may have a, more preferably substituent selected from the group consisting or 2 It has a number of alkyl group having 1 to 8 carbon atoms, and -SO 3 - a phenyl group optionally having a, more preferably one or two alkyl groups having 1 to 4 carbon atoms as a substituent a, and -SO 3 - is a phenyl group which may have a.
  • R 56a in the formula (1t) is a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and an aromatic having 6 to 14 carbon atoms which may have a substituent.
  • R 56a is preferably a halogen atom, an alkyl group and -SO 3 having 1 to 8 carbon atoms - 1 least one substituent a phenyl group which may have a selected from the group consisting of, more preferably a substituent It has a number or two halogen atoms, and -SO 3 - a phenyl group which may have a, more preferably has one or two fluorine atom as a substituent, and -SO 3 - and It is a phenyl group that may have.
  • L 1a in the formula (1t) represents a sulfur atom, an oxygen atom or -NR 57a- .
  • R 57a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • L 1a is preferably a sulfur atom.
  • R in the formula (A3-1) represents an integer of 1 or more. r is preferably 2. When r is an integer of 2 or more, the equation (A3-1a):
  • the rings T 1a , R 41a to R 44a and R 47a to R 54a are synonymous with the above, respectively.
  • the plurality of anions represented by may be the same or different.
  • the anion represented by the formula (A3-1a) may be hereinafter referred to as "anion (A3-1a)".
  • the plurality of anions (A3-1a) are preferably the same.
  • K in the formula (A3-1) are, -SO 3 anion (A3-1a) has - and -SO 2 -N - represents the total number of -SO 2 -R f, and is an integer of 2 or more .. k is preferably 2.
  • Mr + in the formula (A3-1) represents a hydrogen ion, an r-valent metal ion or N + (R 55a ) 4 , and the four R 55a may be the same or different.
  • R 55a represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.
  • k-1 in the formula (A3-1) is an integer of 2 or more, the plurality of Mr + may be the same or different.
  • Mr + is preferably an r-valent metal ion.
  • the r-valent metal ion include alkali metal ions such as lithium ion, sodium ion and potassium ion; alkaline earth metal ions such as beryllium ion, magnesium ion, calcium ion, strontium ion and barium ion; titanium ion and zirconium. Transition metal ions such as ions, chromium ions, manganese ions, iron ions, cobalt ions, nickel ions and copper ions; typical metal ions such as zinc ions, cadmium ions, aluminum ions, indium ions, tin ions, lead ions and bismuth ions. Can be mentioned.
  • Mr + is more preferably a divalent metal ion, more preferably an alkaline earth metal ion, and particularly preferably a barium ion (Ba 2+ ).
  • R 41a and R 43a are independently hydrogen atoms or alkyl groups having 1 to 8 carbon atoms.
  • R 42a and R 44a are each independently an alkyl group and -SO 3 having 1 to 8 carbon atoms - at least one of which may have a substituent phenyl group selected from the group consisting of,
  • R 47a ⁇ R 54a are each independently a hydrogen atom, an alkyl group or -SO 3 having 1 to 8 carbon atoms - and ring T 1a is a ring represented by the above formula (1t) [wherein ( In 1t), R 45a is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • R 46a is an alkyl group and -SO 3 having 1 to 8 carbon atoms - at least one of which may have a substituent phenyl group selected from the group consisting of,
  • R 56a is a halogen atom, an alkyl group and -SO 3 having 1 to 8 carbon atoms - at least one of which may have a substituent phenyl group selected from the group consisting of,
  • L 1a is a sulfur atom, and * represents a bond position with a carbocation.
  • compound (A3-1a) is preferable.
  • R 41a and R 43a are more preferably hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, still more preferably alkyl groups having 1 to 4 carbon atoms, and R 42a and R 44a.
  • R 47a ⁇ R 54a is more preferably a hydrogen atom or -SO 3 - is and, R 45a is more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, R 46a is more preferably a substituent has one or two alkyl groups having 1 to 8 carbon atoms, and -SO 3 - one or two carbon atoms 1 to 4 as a phenyl group optionally, even more preferably substituent having a alkyl group, and -SO 3 - a phenyl group optionally having, as
  • a compound represented by the following formula (A3-1-1) (hereinafter, may be referred to as “compound (A3-1-1)”) is particularly preferable.
  • the two - the description of, -SO 3 as the anion substituent "-SO 3" - has, and -SO 3 in each anion - number of total 2 (i.e., -SO 3 in two anion - total number of 4) meant to be.
  • the compound (A3-1) is a known method (for example, the method described in Journal of Organic Chemistry, (1994), vol. 59, # 11, pp. 3232-3236, the method described in JP-A-2018-127596. ) Can be manufactured.
  • R 41b and R 42b in the formula (A3-2) each independently have a hydrogen atom and a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent which may have a substituent. It represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R 41b and R 42b are bonded to each other. It forms a 3- to 10-membered nitrogen-containing heterocycle with the bonding nitrogen atom.
  • the substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (A3-2) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group. is there.
  • the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (A3-2) is a saturated hydrocarbon group having 2 to 20 carbon atoms
  • -CH 2- contained in the saturated hydrocarbon group is -O-.
  • it may be replaced with -CO-.
  • -CH 2- does not include -CH 2 -bonded to a nitrogen atom and -CH 2- in the methyl group at the end of the saturated hydrocarbon group.
  • -CH 2- CH 2- contained in the saturated hydrocarbon group is not replaced with -O-O- or -CO-CO-.
  • the substituent which the aromatic hydrocarbon group having 6 to 14 carbon atoms in the formula (A3-2) may have has a halogen atom, a nitro group, a hydroxy group, a formyl group, and a substituent. It is at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms.
  • the substituent which may have an aralkyl group having 7 to 30 carbon atoms in the formula (A3-2) is a halogen atom, a nitro group, a hydroxy group, a formyl group, and a carbon which may have a substituent. It is at least one selected from the group consisting of alkyl groups of numbers 1-8.
  • the substituent that the alkyl group having 1 to 8 carbon atoms in the formula (A3-2) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
  • alkyl group having 1 to 8 carbon atoms in the formula (A3-2) is an alkyl group having 2 to 8 carbon atoms
  • -CH 2- contained in the alkyl group is replaced with -O- or -CO-. May be.
  • the -CH 2 - The, -CH 2 in a methyl group is the terminal of the alkyl group - is not included.
  • -CH 2- CH 2- contained in the alkyl group is not replaced with -OO- or -CO-CO-.
  • R 41b is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms.
  • R 42b preferably has a phenyl group which may have an alkyl group having 1 to 8 carbon atoms, more preferably a phenyl group which may have an alkyl group having 1 to 4 carbon atoms, and further preferably a phenyl group. Is.
  • R 43b and R 44b in the formula (A3-2) each independently have a hydrogen atom and a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and a substituent. It represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R 43b and R 44b are bonded to each other. It forms a 3- to 10-membered nitrogen-containing heterocycle with the nitrogen atom.
  • R 43b is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms.
  • R 44b preferably has a phenyl group having 1 to 8 carbon atoms, more preferably a phenyl group having 1 to 4 carbon atoms, and even more preferably a phenyl group. Is.
  • R 47b to R 54b in the formula (A3-2) are alkyl groups having 1 to 8 carbon atoms, which may independently have a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or a substituent. Represents.
  • Each of R 47b to R 54b is independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom.
  • the ring T 1b in the formula (A3-2) may have an aromatic hydrocarbon ring having 6 to 14 carbon atoms which may have a substituent or a 5- to 10-membered aromatic which may have a substituent. Represents a heterocycle.
  • the substituent which the aromatic hydrocarbon ring having 6 to 14 carbon atoms in the formula (A3-2) may have has a halogen atom, a nitro group, a hydroxy group, a formyl group, and a substituent. It is at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms.
  • the substituent which the 5- to 10-membered aromatic heterocycle in the formula (A3-2) may have may have a halogen atom, a nitro group, a hydroxy group, a formyl group, and a substituent. It is at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms.
  • Ring T 1b is preferably of formula (2t):
  • R 45b and R 46b in the formula (2t) may independently have a hydrogen atom and a substituent and may have a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent. It represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R 45b and R 46b are bonded to each other. It forms a 3- to 10-membered nitrogen-containing heterocycle with a nitrogen atom.
  • the substituent that the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (2t) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
  • the substituent which the aromatic hydrocarbon group having 6 to 14 carbon atoms in the formula (2t) may have may have a halogen atom, a nitro group, a hydroxy group, a formyl group and a carbon which may have a substituent. It is at least one selected from the group consisting of alkyl groups of numbers 1-8.
  • the substituent which may have an aralkyl group having 7 to 30 carbon atoms in the formula (2t) may have a halogen atom, a nitro group, a hydroxy group, a formyl group and a substituent having 1 to 1 carbon atoms. At least one selected from the group consisting of 8 alkyl groups.
  • the substituent that the alkyl group having 1 to 8 carbon atoms in the formula (2t) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
  • R 45b is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms.
  • R 46b is preferably a phenyl group which may have an alkyl group having 1 to 8 carbon atoms, more preferably a phenyl group having 1 or 2 alkyl groups having 1 to 8 carbon atoms as a substituent, and further. It is preferably a phenyl group having one or two alkyl groups having 1 to 4 carbon atoms as a substituent.
  • R 56b in the formula (2t) is a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and an aromatic having 6 to 14 carbon atoms which may have a substituent.
  • R 56b is preferably a phenyl group which may have at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 8 carbon atoms, and more preferably one or two substituents.
  • L 1b in the formula (2t) represents a sulfur atom, an oxygen atom or -NR 57b- .
  • R 57b represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • L 1b is preferably a sulfur atom. * In the formula (2t) represents the bonding position with the carbocation.
  • M in the formula (A3-2) represents an integer of 1 or more.
  • m is preferably an integer of 1 to 20, more preferably an integer of 2 to 14, still more preferably an integer of 2 to 8, and particularly preferably 3.
  • rings T 1b , R 41b to R 44b and R 47b to R 54b are synonymous with the above, respectively.
  • the plurality of cations represented by may be the same or different.
  • the cation represented by the formula (A3-2c) may be hereinafter referred to as "cation (A3-2c)".
  • the plurality of cations (A3-2c) are preferably the same.
  • [Y] m- in the formula (A3-2) represents an m-valent anion.
  • [Y] m- is preferably a polyacid anion containing a tungsten atom, more preferably [PW 12 O 40 ] 3- , [P 2 W 18 O 62 ] 6- , [P 2 W 18 O 62].
  • R 41b , R 43b and R 47b to R 54b are independently hydrogen atoms or alkyl groups having 1 to 8 carbon atoms.
  • R 42b and R 44b are phenyl groups which may independently have an alkyl group having 1 to 8 carbon atoms.
  • Ring T 1b is a ring represented by the formula (2t) [in formula (2t), R 45b is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • R 46b is a phenyl group which may have an alkyl group having 1 to 8 carbon atoms.
  • R 56b is a phenyl group which may have at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 8 carbon atoms.
  • L 1b is a sulfur atom, and * represents a bond position with a carbocation.
  • m is 3,
  • a compound in which the three cations (A3-2c) are the same and [Y] m- is [PW 12 O 40 ] 3- (hereinafter sometimes referred to as "compound (A3-2')"). ) Is preferable.
  • R 41b and R 43b are independently, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having a hydrogen atom or 1 to 4 carbon atoms. More preferably, it is an alkyl group having 1 to 4 carbon atoms, and R 42b and R 44b are independent phenyl groups, more preferably having an alkyl group having 1 to 4 carbon atoms, more preferably.
  • R 47b to R 54b are independently, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably a hydrogen atom, and R 45b is more preferably a hydrogen atom or An alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and R 46b more preferably a phenyl having one or two alkyl groups having 1 to 8 carbon atoms as a substituent.
  • compound (A3-2-1) a compound represented by the following formula (A3-2-1) (hereinafter sometimes referred to as “compound (A3-2-1)”) is particularly preferable.
  • the compound (A3-2) can be produced according to a known method (for example, the method described in JP-A-2015-28121).
  • the compound (A3) is mixed with a solvent that does not dissolve the compound (A3) and used as a dispersion liquid of the compound (A3).
  • a dispersant include, for example, those described above for pigment dispersions.
  • the content thereof is preferably 1 part by weight or more and 500 parts by weight or less, more preferably 5 parts by weight, based on 100 parts by weight of compound (A3). More than 300 parts by weight or less.
  • the content of the dispersant is within the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.
  • compound (A3) When compound (A3) is used, its content is preferably 1% by weight or more, more preferably 1.5% by weight or more, and 60% by weight or less, based on the total amount of solids. It is preferably 55% by weight or less, and further preferably 50% by weight or less.
  • the colorant (A) contains a dye (A1) and a compound (A3) different from the compound (A3).
  • the description of the type and content of the dye (A1) in this aspect is as described above.
  • the weight ratio of the dye (A1) to the compound (A3) is preferably 0.5: 99.5 to. It is 99: 1, more preferably 0.5: 99.5 to 95: 5, and particularly preferably 0.5: 95 to 90:10.
  • the resin (B) used in the present invention has the formula (1b):
  • R 1B represents a hydrogen atom or a methyl group.
  • R 2B to R 4B independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
  • n represents an integer from 1 to 10, and * represents the bond position.
  • at least one of R 2B to R 4B is an alkoxy group having 1 to 6 carbon atoms.
  • a resin (B1) containing a structural unit (b1-1) represented by hereinafter, may be referred to as “constituent unit (b1-1)”).
  • the constituent unit (b1-1) may contain only one type, or may contain two or more types.
  • Examples of the alkyl group having 1 to 6 carbon atoms in R 2B to R 4B include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, an isopentyl group and a neopentyl group. Be done.
  • Examples of the alkoxy group having 1 to 6 carbon atoms in R 2B to R 4B include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an isopropoxy group, an isobutoxy group and an isopentyloxy group. , Neopentyloxy group.
  • R 2B to R 4B are independently, preferably a methoxy group, an ethoxy group or a propoxy group, and more preferably a methoxy group or an ethoxy group.
  • n is preferably an integer of 1 to 6, and more preferably an integer of 1 to 3.
  • the resin (B1) is preferably described as a structural unit (b1-1), a structural unit (b1-2) derived from a polymerizable unsaturated compound having an acidic group (hereinafter, “constituent unit (b1-2)”).
  • constituent unit (b1-2) a structural unit derived from a polymerizable unsaturated compound having an acidic group
  • the other structural unit (b1-3) means a structural unit different from the structural unit (b1-1) and the structural unit (b1-2).
  • the resin (B1) which is a copolymer only one kind of the structural unit (b1-1), the structural unit (b1-2) and the structural unit (b1-3) may be contained. Two or more types may be included.
  • the amount of the structural unit (b1-1) when the total of all the structural units in the copolymer is 100 mol% is preferably 1 to 50 mol%, more preferably 5 to 40, from the viewpoint of solvent resistance. It is mol%, more preferably 10 to 30 mol%.
  • the amount of the structural unit (b1-2) when the total of all the structural units in the copolymer is 100 mol% is preferably 10 to 50 mol%, more preferably 15 to 45 mol, from the viewpoint of developability. %, More preferably 20-40 mol%.
  • the amount of the structural units (b1-3) when the total of all the structural units in the copolymer is 100 mol% is preferably 1 to 89 mol%, more preferably 1 to 89 mol%, from the viewpoint of developability and solvent resistance. It is 15 to 80 mol%, more preferably 30 to 70 mol%.
  • the weight average molecular weight (Mw) of the resin (B1) is 1,000 to 50,000, preferably 2,000 to 40,000, and more preferably 3,000 to 30,000 from the viewpoint of developability. is there.
  • the weight average molecular weight (Mw) is a value calculated in terms of polystyrene using gel permeation chromatography (GPC).
  • the silyl group equivalent of the resin (B1) is preferably 400 to 4,000, more preferably 500 to 3,000, from the viewpoint of heat-decomposability, heat-resistant yellowing and solvent resistance.
  • the silyl group equivalent of the resin (B1) is 400 or more, it is effective in further enhancing the heat-resistant decomposition property and heat-resistant yellowing of the colored pattern or the colored coating film.
  • the silyl group equivalent can be calculated from the amount of the monomer charged in the production of the resin (B1).
  • the acid value of the resin (B1) is preferably 20 to 300 mgKOH / g, more preferably 30 to 200 mgKOH from the viewpoint of developability. / G.
  • the acid value of the resin (B1) is a value measured using a mixed indicator of bromothymol blue and phenol red according to JIS K6901 5.3, and is necessary for neutralizing 1 g of the resin (B1). It is a value calculated as the amount of potassium hydroxide (mg), and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.
  • the content of the resin (B1) is preferably 5 to 400 parts by weight, more preferably 5 to 400 parts by weight, based on 100 parts by weight of the polymerizable compound (C), from the viewpoint of forming a good pattern without chipping and peeling after alkaline development. Is 7.5 to 375 parts by weight, more preferably 10 to 350 parts by weight.
  • the resin (B1) has the following formula (2b) in the presence of a solvent:
  • the resin (B1) which is a copolymer
  • a compound (m1-1) and, if necessary, another compound are dissolved in a solvent to prepare a solution, and then a polymerization initiator is added to the solution. It can be produced by reacting at 50 to 130 ° C. for 1 to 20 hours.
  • the resin (B1) which is a copolymer containing the structural unit (b1-1), the structural unit (b1-2) and the structural unit (b1-3), is a compound (m1-1) and an acidic group in the presence of a solvent.
  • Polymerizable unsaturated compound (m1-2) hereinafter sometimes referred to as “compound (m1-2)
  • compound (m1-3) hereinafter “compound (m1-m1-)”
  • the other polymerizable unsaturated compound (m1-3) means a polymerizable unsaturated compound different from the compound (m1-1) and the compound (m1-2).
  • the structural unit (b1-1) is derived from the compound (m1-1)
  • the structural unit (b1-2) is derived from the compound (m1-2)
  • the structural unit (b1-3) is derived from the compound (m1-m1-). Derived from 3).
  • the resin (B1) which is a copolymer, is obtained by dissolving, for example, compound (m1-1), compound (m1-2) and compound (m1-3) in a solvent to prepare a solution, and then polymerizing the solution. It can be produced by adding an initiator and reacting at 50 to 130 ° C. for 1 to 20 hours.
  • Examples of the compound (m1-1) include 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- Examples thereof include (meth) acryloyloxypropyl ethyldiethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, and 3- (meth) acryloyloxypropyltriethoxysilane.
  • 3- (meth) acryloyloxypropyltrimethoxysilane and 3- (meth) acryloyloxypropyltriethoxysilane are preferable from the viewpoint of availability and reactivity.
  • "3- (meth) acryloyloxypropylmethyldimethoxysilane” means at least one selected from 3-acryloyloxypropylmethyldimethoxysilane and 3-methacryloyloxypropylmethyldimethoxysilane. Other similar statements have the same meaning.
  • Examples of the compound (m1-2) include (meth) acrylic acid, crotonic acid, cinnamic acid, vinyl sulfonic acid, 2- (meth) acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, and 2- (meth). ) Acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl acid phosphate and the like.
  • (meth) acrylic acid is preferable from the viewpoint of availability and reactivity.
  • Examples of the compound (m1-3) include the following: butadiene; Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylic rate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) ) Acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, benzyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, lauryl ( Meta) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohe
  • the compound (m1-3) includes methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like.
  • Glycidyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, (meth) acrylate N, N-dimethylamide, (meth) acrylic morpho Phosphorus, styrene, vinyltoluene and norbornene are preferred, methyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, glycidyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (3-ethyloxetane-3-yl) methyl ( Meta) Acrylate, styrene and vinyl toluene are more preferred.
  • the compound (m1-3) is preferably an alkyl (meth) acrylate, more preferably a methyl (meth) acrylate, a benzyl (meth) acrylate, or a dicyclopentanyl (meth) acrylate. preferable.
  • the compound (m1-3) is preferably a polymerizable compound having a functional group (for example, glycidyl group, oxetaneyl group, isocyanato group, block isocyanato group) that reacts with an acidic group, and glycidyl (for example). More preferred are meta) acrylates and (3-ethyloxetane-3-yl) methyl methacrylate.
  • a functional group for example, glycidyl group, oxetaneyl group, isocyanato group, block isocyanato group
  • glycidyl for example. More preferred are meta) acrylates and (3-ethyloxetane-3-yl) methyl methacrylate.
  • Examples of the blocking agent used for blocking the above-mentioned isocyanato group include the following: Lactam-based blocking agents such as ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, ⁇ -propiolactam; Alcohol-based blocking agents such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, cyclohexanol; Butylphenol such as phenol, cresol, xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, oxybenzoic acid ester, timole, p-naphthol
  • -Phenol-based blocking agents such as nitrophenol and p-chlorophenol; Active methylene block agents such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone; Mercaptan-based blocking agents such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan; Amine-based blocking agents such as diphenylamine, phenylnaphthylamine, aniline, and carbazole; Acid amide blocking agents such as acetanilide, acetanilide, acetate amide, benzamide; Acid-imide-based blocking agents such as succinate imide and maleate imide; Imidazole-based blocking agents such as imidazole, 2-methylimidazole, and 2-ethylimidazole; Urea-based blocking agents such as urea, thiourea, and ethylene
  • the solvent used for the polymerization has 3 to 3 carbon atoms. It preferably contains 10 hydroxy group-containing solvents. Examples of the hydroxy group-containing solvent having 3 to 10 carbon atoms include monoalcohols such as propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol and benzyl alcohol; ethylene glycol monomethyl ether and ethylene.
  • Glycol monoethyl ether diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol
  • Examples thereof include (poly) alkylene glycol monoalkyl ethers such as monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether and tripropylene glycol monomethyl ether.
  • the solvent used for the polymerization may contain a solvent other than the hydroxy group-containing solvent having 3 to 10 carbon atoms.
  • the solvent include (poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether and diethylene glycol methyl.
  • Ethers such as ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, butyl acetate, propyl acetate, isopropyl acetate, acetic acid Butyl, isobutyl acetate, amyl acetate, isoamyl acetate, butyl propionate, ethyl butyrate, propyl butyrate, isoprop
  • the content of the hydroxy group-containing solvent having 3 to 10 carbon atoms with respect to the entire solvent used for the polymerization is 10 to 100% by weight from the viewpoint of controlling the weight molecular weight and the molecular weight distribution (Mw / Mn) of the resin (B1). It is preferably 20 to 100% by weight, and more preferably 20 to 100% by weight.
  • the amount of the solvent used in the polymerization is not particularly limited, but is preferably 30 to 30 parts by weight based on 100 parts by weight of the total amount of the compound (m1-1), the compound (m1-2) and the compound (m1-3). It is 1,000 parts by weight, more preferably 50 to 800 parts by weight.
  • the polymerization initiator that can be used for the polymerization is not particularly limited, and is, for example, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2, Examples thereof include 2'-azobis (isobutyric acid) dimethyl, benzoyl peroxide, and tert-butylperoxy-2-ethylhexanoate.
  • the amount of the polymerization initiator used is not particularly limited, but is preferably 0.5 with respect to 100 parts by weight of the total amount of the compound (m1-1), the compound (m1-2) and the compound (m1-3) used. It is ⁇ 20 parts by weight, more preferably 1.0 to 10 parts by weight.
  • the resin (B1) is preferably a copolymer of (meth) acrylic acid, 3- (meth) acryloyloxypropyltrimethoxysilane and methyl (meth) acrylate.
  • the resin (B1) is preferably a copolymer of (meth) acrylic acid, 3- (meth) acryloyloxypropyltriethoxysilane and dicyclopentanyl (meth) acrylate. ..
  • the resin (B) may contain a resin (B2) different from the resin (B1).
  • the resin (B2) is preferably an alkali-soluble resin, and is at least one monomer selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter, "monomer (m2-1)"). It is preferable that the polymer contains a structural unit derived from (may be described as). In the polymer, the structural unit may contain only one type, or may contain two or more types.
  • the resin (B2) is a monomer having a structural unit derived from the monomer (m2-1), a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond (hereinafter, “monomer (m2-)”. It is more preferable that the copolymer contains a structural unit derived from (2) ”.
  • the copolymer may contain other structural units. As other structural units, for example, a monomer (m2-1) and a monomer different from the monomer (m2-2) (hereinafter, "monomer (m2-3)" may be described. ), A structural unit having an ethylenically unsaturated bond, and the like.
  • each of the constituent units may contain only one type, or may contain two or more types.
  • Examples of the monomer (m2-1) include the following: Acrylic acid, methacrylic acid, crotonic acid and unsaturated monocarboxylic acids such as o-, m-, p-vinylbenzoic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexendicarboxylic acid; Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, Bicyclounsaturated compounds containing carboxy groups such as 5-carboxymethylbicyclo
  • acrylic acid, methacrylic acid and maleic anhydride are preferable from the viewpoint of reactivity and the solubility of the obtained resin in an alkaline aqueous solution.
  • the monomer (m2-2) refers to a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond.
  • the monomer (m2-2) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.
  • Examples of the cyclic ether structure having 2 to 4 carbon atoms include an oxylan ring, an oxetane ring, and a tetrahydrofuran ring.
  • Examples of the monomer (m2-2) include a monomer having an oxylanyl group and an ethylenically unsaturated bond (hereinafter, may be referred to as “monomer (m2-2-1)”), and oxetanyl.
  • a monomer having a group and an ethylenically unsaturated bond hereinafter sometimes referred to as “monomer (m2-2-2)
  • a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond hereinafter, it may be described as “monomer (m2-2-3)
  • monomer (m2-2-3) monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond
  • the monomer (m2-2-1) for example, a monomer having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter, “monomer (m2-2)”. -1a) ”) and a monomer having an alicyclic unsaturated hydrocarbon epoxidized structure (hereinafter, may be described as“ (monomer m2-2-1b) ”. ).
  • the monomer (m2-2-1a) a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable.
  • the monomer (m2-2-1a) include glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, ⁇ -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, vinylbenzyl glycidyl ether, and ⁇ -methyl.
  • Examples of the monomer (m2-2-1b) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, celloxide® 2000; manufactured by Daicel), 3,4-epoxy. Cyclohexylmethyl (meth) acrylate (eg, Cyclomer® A400; manufactured by Daicel), 3,4-epoxycyclohexylmethyl (meth) acrylate (eg, Cyclomer® M100; manufactured by Daicel), formula. Examples thereof include a compound represented by (BI) and a compound represented by the formula (BII).
  • Ra and R b each independently represent an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydrogen atom or a hydroxy group.
  • X a and X b are each independently a single bond, * - R c -, * - R c -O -, * - R c -S- or * -R c -NH- the stands, R c represents an alkanediyl group having 1 to 6 carbon atoms, and * represents a bond position with O.
  • Examples of the compound represented by the formula (BI) include compounds represented by any of the formulas (I-1) to (I-15). Among them, formulas (I-1), formulas (I-3), formulas (I-5), formulas (I-7), formulas (I-9) and formulas (I-11) to formulas (I-15).
  • the compound represented by any of the above is preferable, and the compound represented by any of the formula (I-1), the formula (I-7), the formula (I-9) and the formula (I-15) is more preferable.
  • Examples of the compound represented by the formula (BII) include compounds represented by any of the formulas (II-1) to (II-15). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) and formula (II-11) to formula (II-15).
  • the compound represented by any of the above is preferable, and the compound represented by any of the formula (II-1), the formula (II-7), the formula (II-9) and the formula (II-15) is more preferable.
  • the compound represented by the formula (BI) and the compound represented by the formula (BII) may be used independently, respectively, and the compound represented by the formula (BI) and the compound represented by the formula (BII) may be used alone. May be used in combination with. When these are used in combination, the molar ratio of the compound represented by the formula (BI) and the compound represented by the formula (BII) (the compound represented by the formula (BI): the compound represented by the formula (BII)) is used. It is preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and even more preferably 20:80 to 80:20.
  • Examples of the monomer (m2-3) include the following: Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, Lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan-9-yl (meth) acrylate, tricyclo [5.2.1.0 2,6] decene-8-yl (meth) acrylate, tricyclo [5.2.1.0 2,6] Decene-9-yl (meth) acrylate, dicyclopentanyloxye
  • the monomers (m2-3) include styrene, vinyltoluene, tricyclo [5.2.1.0 2,6 ] decane-8-yl (meth) acrylate, and tricyclo [ 5.2.1.0 2,6 ] Decan-9-yl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] Desen-8-yl (meth) acrylate, tricyclo [5.2.
  • the structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth) acryloyl group.
  • the resin (B2) having such a structural unit is a polymer containing a structural unit derived from the monomer (m2-1) and a structural unit derived from the monomer (m2-2). It can be obtained by adding a group capable of reacting with the group having the group and a monomer having an ethylenically unsaturated bond.
  • the structural unit having an ethylenically unsaturated bond for example, a structural unit obtained by adding glycidyl (meth) acrylate to the (meth) acrylic acid unit, and 2-hydroxyethyl (meth) acrylate as the maleic anhydride unit.
  • Constituent units obtained by addition structural units obtained by adding (meth) acrylic acid to glycidyl (meth) acrylate units, and structural units obtained by adding carboxylic acid anhydride to structural units having a hydroxy group. Units and the like can be mentioned.
  • a polymer containing a structural unit derived from the monomer (m2-1) can be produced, for example, by polymerizing the monomer constituting the structural unit of the polymer in a solvent in the presence of a polymerization initiator.
  • the polymerization initiator, solvent and the like are not particularly limited, and those usually used in the art can be used.
  • the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.).
  • the solvent is not particularly limited as long as it dissolves each monomer, and examples thereof include the solvent (H) described later.
  • the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or the polymer is taken out as a solid (powder) by a method such as reprecipitation. May be used.
  • a carboxylic acid anhydride having an ethylenically unsaturated bond may be used as the monomer.
  • the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic acid anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, and the like. Examples thereof include 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride.
  • Examples of the resin (B2) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxytricyclo [5.2.1.0 2,6 ] decyl.
  • the combination is a copolymer of 3,4-epoxytricyclo [5.2.1.0 2,6 ] decyl (meth) acrylate / (meth) acrylic acid.
  • the weight average molecular weight (Mw) of the resin (B2) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. ..
  • the molecular weight distribution (Mw / Mn) (that is, the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn)) of the resin (B2) is preferably 1.1 to 6, more preferably 1.2 to 1. It is 4.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin (B2) are values calculated in terms of polystyrene using gel permeation chromatography (GPC).
  • the acid value (solid content conversion value) of the resin (B2) is preferably 10 to 300 mgKOH / g, more preferably 20 to 250 mgKOH / g, even more preferably 20 to 200 mgKOH / g, still more preferably 20 to 170 mgKOH / g. It is even more preferably 30 to 170 mgKOH / g, particularly preferably 50 to 150 mgKOH / g, even more preferably 60 to 140 mgKOH / g, and most preferably 60 to 135 mgKOH / g.
  • the acid value of the resin (B2) is a value calculated as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B2), for example, by titrating with an aqueous potassium hydroxide solution. Can be sought.
  • its content with respect to 100 parts by weight of the colorant (A) is preferably 1 to 1,200 parts by weight, more preferably 5 to 1,000 parts by weight, and further preferably. Is 10 to 800 parts by weight.
  • the resin (B2) When the resin (B2) is used, its content with respect to the total solid content is preferably 1 to 50% by weight, more preferably 1 to 45% by weight, still more preferably 1 to 40% by weight, and most preferably 1 to 1 to 40% by weight. It is 30% by weight.
  • the polymerizable compound (C) is a compound that can be polymerized by active radicals and / or acids generated from the polymerization initiator (D).
  • the polymerizable compound (C) is preferably a radically polymerizable compound.
  • Examples of the radically polymerizable compound include compounds having a polymerizable ethylenically unsaturated bond.
  • the radically polymerizable compound is preferably (meth) acrylates.
  • Examples of the polymerizable compound (C) include the following: Compounds having one ethylenically unsaturated bond such as nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone; 1,6-Hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bisphenol A bis (acryloyloxyethyl) ether and Compounds with two ethylenically unsaturated bonds, such as 3-methylpentanediol di (meth) acrylate; Compounds with three ethylenically unsaturated bonds such as trimethylolpropane tri (meth) acrylate, pent
  • a compound having seven or more ethylenically unsaturated bonds such as tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, and tetrapentaerythritol deca (meth) acrylate.
  • the polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds, and more preferably a polymerizable compound having 5 or 6 ethylenically unsaturated bonds.
  • dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.
  • KAYARAD registered trademark
  • DPHA Nippon Kayaku Co., Ltd.
  • A-TMM-3LM-N Shin-Nakamura Chemical Co., Ltd.
  • A9550 Shin-Nakamura Chemical Co., Ltd.
  • the molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 or more and 1,500 or less.
  • the molecular weight of the polymerizable compound (C) of 1,000 or more is a weight average molecular weight (Mw) calculated in terms of polystyrene using gel permeation chromatography (GPC).
  • the content of the polymerizable compound (C) is preferably 7 to 65% by weight, more preferably 13 to 60% by weight, still more preferably 17 to 55% by weight, based on the total amount of solids.
  • the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming the coloring pattern and the chemical resistance of the color filter tend to be improved.
  • the weight ratio of the resin (B) to the polymerizable compound (C) is preferably 20:80 to 80:20, more preferably 35:65. ⁇ 80:20.
  • the polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization by generating active radicals, acids and the like by the action of light or heat, and a known polymerization initiator can be used.
  • the polymerization initiator (D) is preferably a photoradical polymerization initiator.
  • the polymerizable compound (C) is a radically polymerizable compound, and the polymerization initiator (D) is a photoradical polymerization initiator (that is, the colored curable resin composition of the present invention is a photocurable resin. It is a composition) is more preferable.
  • the photoradical polymerization initiator is preferably at least one selected from the group consisting of an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound and a biimidazole compound, and more preferably an O-acyloxime compound. Is.
  • the O-acyloxime compound is a compound having a partial structure represented by the formula (d1) (in the following formula, * represents a binding position).
  • O-acyloxym compound examples include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-.
  • TR-PBG327 manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.
  • Irgacure (registered trademark) OXE01 Irgacure (registered trademark) OXE02
  • Irgacure (registered trademark) OXE03 Irgacure (registered trademark) OXE04
  • N- Commercially available products such as 1919 (manufactured by ADEKA) may be used.
  • the O-acyloxime compounds are TR-PBG327 (manufactured by Joshu Strong Electronics New Materials Co., Ltd.), Irgacure (registered trademark) OXE01, Irgacure (registered trademark) OXE02, Irgacure (registered trademark) OXE03, Irgacure (registered trademark) OXE04 (registered trademark).
  • N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one
  • At least one selected from the group consisting of -2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine is preferred, and TR-PBG327 (Tsunshu strong electron) New Materials Co., Ltd.)
  • Irgacure (registered trademark) OXE01 Irgacure (registered trademark) OXE02
  • Irgacure (registered trademark) OXE03 Irgacure (registered trademark) OXE04 (above, manufactured by BASF)
  • the alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3) (in the following formula, * represents a bond position).
  • the benzene ring may have a substituent.
  • Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4). -Morphorinophenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one And so on.
  • Irgacure registered trademark
  • Irgacure registered trademark
  • Irgacure registered trademark
  • Irgacure registered trademark
  • Irgacure registered trademark
  • Irgacure registered trademark
  • Irgacure registered trademark
  • Irgacure registered trademark
  • Irgacure registered trademark
  • Irgacure registered trademark
  • Irgacure registered trademark
  • Irgacure registered trademark 379
  • examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2).
  • the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).
  • triazine compound examples include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-methoxy).
  • acylphosphine oxide compound examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
  • Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.
  • biimidazole compound examples include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl) -4.
  • Examples of the other polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4 -Benzoyl-4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenance Kinone compounds such as lenquinone, 2-ethylanthraquinone, and camphorquinone; examples thereof include 10-butyl-2-chloroacrydone, benzyl, methyl phenylglycoxylate, and titanosen compounds. These are preferably used in combination with the polymerization initiator (F) (particularly
  • Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethyl.
  • Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyltosylate, benzoin Examples include tosilates.
  • the content of the polymerization initiator (D) is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the total of the resin (B) and the polymerizable compound (C). It is a department.
  • the content of the polymerization initiator (D) is within the above range, the sensitivity of the color curable resin composition of the present invention tends to be improved and the exposure time tends to be shortened, so that the productivity of the color filter is increased. improves.
  • One of the features of the colored curable resin composition of the present invention is that it contains a phenolic antioxidant (E).
  • the phenolic antioxidant (E) it is possible to suppress a decrease in the thickness of the colored pattern or the colored coating film due to heating (particularly post-baking). Further, by using the phenolic antioxidant (E), the heat resistance of the colored pattern or the colored coating film can be improved.
  • the "phenolic antioxidant” means an antioxidant having a phenolic hydroxyl group. Therefore, for example, an antioxidant containing both a phenolic hydroxyl group and a phosphorus atom is classified as a phenolic antioxidant, not a phosphorus-based antioxidant, in the present specification.
  • the phenolic antioxidant in the present specification also includes an antioxidant having a protected phenolic hydroxyl group (hereinafter, may be referred to as "protected phenolic antioxidant").
  • phenolic antioxidants include: (1) Alkylthiomethylphenol 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6- Didodecylthiomethyl-4-nonylphenol.
  • O-benzyl derivative, N-benzyl derivative and S-benzyl derivative 3,5,3', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3 , 5-Dimethylbenzyl mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.
  • Aromatic hydroxybenzyl derivative 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,4-bis (3,5) -Di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-tert-butyl-4-hydroxybenzyl) phenol.
  • Benzylphosphonate derivative dimethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di -Calc of tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoester salt.
  • esters of ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid and the following monohydric or polyhydric alcohols Methanol, ethanol, octanol, octadecanol, ethylene glycol, 1, 3-Propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) ) Isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6 , 7-Trioxabi
  • esters of ⁇ - (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid and the following monohydric or polyhydric alcohols Methanol, ethanol, octanol, octadecanol, ethylene glycol, 1, 3-Propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) ) Isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6 , 7-Trioxabicyclo
  • esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid and the following monohydric or polyhydric alcohols Methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N , N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxa Bicyclo [2,2,2] oc
  • the phenolic hydroxyl group of the above-exemplified phenolic antioxidant protected with a protecting group can also be used as the phenolic antioxidant in the present invention.
  • the protecting group include ether-based protecting groups, acetal-based protecting groups, acyl-based protecting groups, and silyl ether-based protecting groups.
  • the ether-based protecting group include a methyl group, a benzyl group, a p-methoxybenzyl group, and a tert-butyl group.
  • Examples of the acetal-based protecting group include a methoxymethyl group, a 2-tetrahydropyranyl group, and an ethoxyethyl group.
  • Examples of the acyl-based protecting group include an acetyl group, a pivaloyl group, and a benzoyl group.
  • Examples of the silyl ether-based protecting group include a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a triisopropylsilyl group, and a tert-butyldiphenylsilyl group.
  • a tert-butoxycarbonyl (Boc) group may be used as the protecting group.
  • the Boc group is preferable as the protecting group for the phenolic hydroxyl group.
  • phenolic antioxidants examples include Sumilyzer (registered trademark) GP (manufactured by Sumitomo Chemical Co., Ltd.) and ADEKA STAB (registered trademark) AO series (manufactured by ADEKA).
  • commercially available products of the protected phenolic antioxidant include, for example, ADEKA ARKULS® GPA-5001 (manufactured by ADEKA).
  • the content of the phenolic antioxidant (E) is 100 parts by weight of the polymerizable compound (C) from the viewpoint of suppressing the decrease in the thickness of the colored pattern or the colored coating film due to heating and obtaining a good coloring pattern after alkaline development.
  • it is preferably 0.1 to 25 parts by weight, more preferably 0.2 to 20 parts by weight, still more preferably 0.5 to 20 parts by weight, and particularly preferably 3 to 10 parts by weight.
  • the colored curable resin composition of the present invention may further contain a polymerization initiator (F).
  • the polymerization initiator (F) is a compound or a sensitizer used to promote the polymerization of a polymerizable compound whose polymerization has been initiated by the polymerization initiator.
  • Examples of the polymerization initiator (F) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds and carboxylic acid compounds.
  • Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and the like.
  • 2-Ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4' -Bis (ethylmethylamino) benzophenone and the like can be mentioned.
  • 4,4'-bis (diethylamino) benzophenone is preferable.
  • the amine compound a commercially available product such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.
  • alkoxyanthracene compound examples include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-.
  • examples thereof include dibutoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.
  • thioxanthone compound examples include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.
  • carboxylic acid compound examples include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, and dichlorophenylsulfanyl acetic acid.
  • N-phenylglycine phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.
  • the polymerization initiator (F) is preferably a thioxanthone compound, more preferably 2,4-diethylthioxanthone.
  • the content of the resin (B) and the polymerizable compound (C) with respect to 100 parts by weight is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight. It is a department.
  • its content with respect to 100 parts by weight of the polymerization initiator (D) is preferably 5 to 80 parts by weight, more preferably 10 to 60 parts by weight, and further preferably 15 to 15 parts by weight. It is 55 parts by weight.
  • the amount of the polymerization initiator (F) is within the above range, a coloring pattern can be formed with high sensitivity, and the productivity of the color filter tends to be improved.
  • the colored curable resin composition of the present invention may further contain a thiol compound (G).
  • the thiol compound (G) is a compound having a sulfanil group (-SH).
  • Examples of the compound having one sulfanyl group include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanylbenzoxazole, 2-sulfanylnicotinic acid, and 2-sulfanyl.
  • Compounds having two or more sulfanyl groups include, for example, hexanedithiol, decandithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanyl propionate), butanediol bis (3-sulfanyl).
  • the thiol compound (G) is preferably a compound having two or more sulfanil groups, and more preferably trimethylolpropane tris (3-sulfanil propionate).
  • the thiol compound (G) When the thiol compound (G) is used, its content is preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the polymerizable compound (C). When the content of the thiol compound (G) is within this range, the sensitivity tends to be high and the developability tends to be good.
  • the colored curable resin composition of the present invention may further contain a solvent (H).
  • the solvent (H) is not particularly limited, and a solvent usually used in the art can be used.
  • Examples of the solvent (H) include an ester solvent (a solvent containing -COO- in the molecule and not containing -O-) and an ether solvent (a solvent containing -O- in the molecule and not containing -COO-).
  • Ether ester solvent solvent containing -COO- and -O- in the molecule
  • ketone solvent solvent containing -CO- in the molecule and not containing -COO-
  • alcohol solvent OH in the molecule
  • the concept of "-O-” does not include “-O-" in "-COO-”
  • the concept of "-CO-” includes “-CO-" in "-COO-”. Is not included.
  • ester solvent examples include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and the like.
  • ester solvent examples include butyl butylate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and ⁇ -butyrolactone.
  • ether solvent examples 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, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol mono.
  • ether ester solvent examples include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -Ethyl ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methylpropionic acid Methyl, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoe
  • ketone solvent examples include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, diacetone alcohol, and cyclo.
  • examples include pentanone, cyclohexanone and isophorone.
  • alcohol solvent examples include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.
  • aromatic hydrocarbon solvent examples include benzene, toluene, xylene and mesitylene.
  • amide solvent examples include N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.
  • the solvent (H) an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm is preferable from the viewpoint of coatability and dryness.
  • the solvent (H) include 3-methoxy-1-butanol, 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 monoethyl ether.
  • Diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide are preferable, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diacetone alcohol. And ethyl 3-ethoxypropionate are more preferred.
  • the solvent (H) When the solvent (H) is used, its content is preferably 35 to 95% by weight, more preferably 40 to 92% by weight, based on the entire colored curable resin composition of the present invention. In other words, the total solid content of the colored curable resin composition is preferably 5 to 65% by weight, more preferably 8 to 60% by weight.
  • the content of the solvent (H) is within the above range, the flatness at the time of coating is good, and the display characteristics tend to be good because the color density is not insufficient when the color filter is formed. ..
  • the colored curable resin composition of the present invention may contain a leveling agent (I).
  • a leveling agent (I) examples include silicone-based surfactants and fluorine-based surfactants. These may have a polymerizable group in the side chain.
  • silicone-based surfactant examples include a surfactant having a siloxane bond in the molecule.
  • examples of commercially available products include Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (manufactured by Toray Dow Corning), KP321, KP322, KP323, KP324, and KP326.
  • TSF400 TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan GK) and the like.
  • the silicone-based surfactant may have a fluorine atom.
  • examples of the silicone-based surfactant having a fluorine atom include Megafuck (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).
  • fluorine-based surfactant examples include a surfactant having a fluorocarbon chain in the molecule.
  • examples of commercially available products include Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Megafuck (registered trademark) F142D, F171, F172, F173, F177, F183, and F554.
  • R30, RS-718-K (manufactured by DIC), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.), Surflon (registered trademark) S381, S382, Examples thereof include SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).
  • the leveling agent (I) When the leveling agent (I) is used, its content is preferably 0.001% by weight or more and 0.2% by weight or less, and more preferably 0.002% by weight, based on the entire colored curable resin composition. % Or more and 0.1% by weight or less, more preferably 0.01% by weight or more and 0.05% by weight or less. It should be noted that this content does not include the content of the dispersant used in the production of the pigment dispersion liquid. When the content of the leveling agent (I) is within the above range, the flatness of the color filter can be improved.
  • the color curable resin composition of the present invention contains additives known in the art such as fillers, other polymer compounds, adhesion promoters, light stabilizers, chain transfer agents, etc., if necessary. May be good.
  • the color curable resin composition of the present invention includes, for example, a colorant (A), a resin (B) (resin (B1) and, if necessary, a resin (B2)), a polymerizable compound (C), and a polymerization initiator ( By mixing D) and a phenolic antioxidant (E) and, if necessary, a solvent (H), a leveling agent (I), a polymerization initiator (F), a thiol compound (G) and other components. Can be prepared.
  • the pigment (A2) When the pigment (A2) is used, the pigment (A2) is mixed with a part or all of the solvent (H) in advance, and a bead mill or the like is used until the average particle size of the pigment (A2) is about 0.2 ⁇ m or less. It is preferable to disperse the pigment (A2) to prepare a pigment dispersion liquid. At this time, if necessary, a dispersant and a part or all of the resin (B) (particularly the resin (B2)) may be blended.
  • the desired color-curable resin composition can be prepared by mixing the remaining components with the pigment dispersion liquid thus obtained so as to have a predetermined concentration.
  • the dye (A1) When the dye (A1) is used, the dye (A1) may be dissolved in a part or all of the solvent (H) in advance to prepare a dye solution. It is preferable to filter the solution with a filter having a pore size of about 0.01 to 1 ⁇ m. Further, it is preferable to filter the colored curable resin composition obtained by mixing the above components with a filter having a pore size of about 0.01 to 10 ⁇ m.
  • Examples of the method for forming a color filter from the colored curable resin composition of the present invention include a photolithography method and a method using an inkjet device.
  • a color-curable resin composition is usually applied onto a substrate, and volatile components such as a solvent are removed by heat drying (prebaking) and / or vacuum drying to form a composition layer to form a photomask.
  • prebaking heat drying
  • / or vacuum drying vacuum drying
  • post-baking is often performed to heat the coloring pattern.
  • a colored coating film which is a cured product of the composition layer can be formed.
  • the colored pattern and colored coating film thus obtained can be used as a color filter.
  • the substrate examples include a glass plate, a resin plate, a silicon plate, and the like.
  • An aluminum, silver, silver / copper / palladium alloy thin film or the like may be formed on the substrate.
  • another color filter layer, resin layer, transistor, circuit or the like may be formed on the substrate.
  • the thickness of the color filter to be produced is not particularly limited and can be appropriately adjusted according to the intended use and the like, and is, for example, 0.1 to 30 ⁇ m, preferably 1 to 20 ⁇ m, and more preferably 1 to 6 ⁇ m.
  • the formation of colored patterns (pixels) by the photolithography method can be performed with known or conventional devices and conditions.
  • the coloring pattern can be formed as follows.
  • a colored curable resin composition is applied onto a substrate, and volatile components such as a solvent are removed by heat drying (prebaking) and / or vacuum drying to obtain a smooth composition layer.
  • the coating method include a spin coating method, a slit coating method, a slit and spin coating method, and the like.
  • the composition layer is irradiated with light through a photomask for forming a desired coloring pattern (exposure).
  • An exposure device such as a mask aligner and a stepper should be used because it is possible to uniformly irradiate the entire exposed surface with parallel light rays and accurately align the photomask with the substrate on which the composition layer is formed. Is preferable.
  • a colored pattern is formed on the substrate by bringing the exposed composition layer into contact with a developing solution (development).
  • development By development, the unexposed portion of the composition layer is dissolved in a developing solution and removed.
  • an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable.
  • the developing method may be any of a paddle method, a dipping method, a spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.
  • the color filter produced from the colored curable resin composition of the present invention is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.
  • display devices for example, liquid crystal display devices, organic EL devices, electronic paper, etc.
  • solid-state image sensors for example, liquid crystal display devices, organic EL devices, electronic paper, etc.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the production example were measured by using GPC under the following conditions.
  • the ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight and the number average molecular weight obtained above was used as the molecular weight distribution.
  • ⁇ Manufacturing example 2 Production of resin (B1-2)> 750.0 g of propylene glycol monomethyl ether was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introduction tube, and the mixture was stirred while replacing nitrogen, and the temperature was raised to 80 ° C. Next, a monomer consisting of 39.2 g (0.46 mol) of methacrylic acid, 132.0 g (0.46 mol) of 3-methacryloyloxypropyltriethoxysilane and 50.1 g (0.23 mol) of dicyclopentanyl methacrylate.
  • the resin (B2-1) has the following structural units (in the following formula, * indicates a bonding position).
  • the red pigment used in the production of the dispersion liquid of the red pigment was synthesized as follows.
  • Sodium tert-amyl alcoholate was synthesized by reacting 174 g of tert-amyl alcohol with 22.2 g of metallic sodium at 130 ° C. under a nitrogen atmosphere. This was heated to 60 ° C., 91.0 g of 4-bromobenzonitrile, 71.05 g of di-tert-amyl ester succinate, and 108.9 g of tert-amyl alcohol were added, and the temperature of the obtained suspension was 85. The suspension was stirred for 2 hours so that the temperature was below ° C. This suspension was stirred as it was at 85 ° C.
  • the compound (A3-1-1) is a dye that dissolves in diacetone alcohol.
  • propylene glycol monomethyl ether acetate is used. It was used to produce a dispersion of compound (A3-1-1), which was used.
  • the compound (A3-2-1) is a dye that dissolves in diacetone alcohol.
  • propylene glycol monomethyl ether acetate is used. It was used to produce a dispersion of compound (A3-2-1), which was used.
  • Examples 1 to 16 and Comparative Examples 1 to 5 (1) Production of Color Curable Resin Composition Each component was mixed so as to have the compositions shown in Tables 1 to 3 below to obtain a color curable resin composition.
  • the components used in the production of the color curable resin composition are as follows. ⁇ Dye (A1)> (A1-1): Dye represented by the following formula (A1-1) obtained by the method described in Example 1 of JP-A-2016-27075 (A1-2): Example 2 of JP-A-2017-226814. Dye represented by the following formula (A1-2) obtained by the method described in (A1-3): The following formula (A1-3) obtained by the method described in Synthesis Example 2 of JP-A-2016-176075. Dye represented by
  • D-1 Compound represented by the following formula (D-1) (“TR-PBG327” manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.)
  • D-2) BASF's "Irgacure (registered trademark) 907"
  • TPP Triphenyl phosphate
  • ADEKA STAB registered trademark TPP
  • H-1 3-Methoxy-1-butanol (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 158 ° C.)
  • H-2 Diacetone alcohol (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 168 ° C)
  • H-3 Propylene glycol monomethyl ether acetate (manufactured by KH Neochem, 146 ° C)
  • H-4 Propylene glycol monomethyl ether (manufactured by KH Neochem, boiling point 121 ° C.)
  • a colored curable resin composition is applied on a 2-inch square glass substrate (Eagle 2000; manufactured by Corning Inc.) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes. To form a composition layer. After cooling, the composition layer was irradiated with light at an exposure amount of 60 mJ / cm 2 (based on 365 nm) in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon). After light irradiation, a colored coating film was obtained by post-baking at 230 ° C. for 20 minutes in an oven. After allowing to cool, the thickness of the obtained colored coating film was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.) and found to be 3.0 ⁇ m.
  • DEKTAK3 film thickness measuring device
  • Thickness retention rate (%) (thickness after post-baking / thickness before post-baking) x 100
  • the thickness retention rate was calculated according to. The results are shown in Tables 1 to 3.
  • the color filter produced from the colored curable resin composition of the present invention is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

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Abstract

A colored curable resin composition including a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), wherein the colored curable resin composition also includes a phenolic antioxidant (E), and the resin (B) includes a resin (B1) including a structural unit (b1-1) represented by formula (1b) [the symbols in the formula are as defined in the specification.].

Description

着色硬化性樹脂組成物Color curable resin composition
　本発明は、着色硬化性樹脂組成物に関する。 The present invention relates to a colored curable resin composition.
　着色硬化性樹脂組成物は、液晶表示装置、エレクトロルミネッセンス表示装置およびプラズマディスプレイ等の表示装置に使用されるカラーフィルタの製造に用いられており、様々な樹脂組成物が開発されている。例えば、特許文献１には、溶剤、反応性希釈剤、光重合開始剤、着色剤、および式（１）： Color curable resin compositions are used in the manufacture of color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays, and various resin compositions have been developed. For example, Patent Document 1 describes a solvent, a reactive diluent, a photopolymerization initiator, a colorant, and the formula (1):
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
［式（１）中の記号の定義は特許文献１の記載の通りである。］
で表される構成単位を含む共重合体を含むカラーフィルタ用樹脂組成物が記載されている。 [Definition of symbols in formula (1) is as described in Patent Document 1. ]
A resin composition for a color filter containing a copolymer containing a structural unit represented by is described.
ＷＯ　２０１８／１１００９７　Ａ１WO 2018/11007 A1
　着色硬化性樹脂組成物によりカラーフィルタを形成する方法としては、例えば、フォトリソグラフ法およびインクジェット機器を用いる方法が挙げられる。フォトリソグラフ法では、通常、着色硬化性樹脂組成物を基板上に塗布し、加熱乾燥（プリベーク）および／または減圧乾燥によって溶剤等の揮発成分を除去して組成物層を形成し、該組成物層に光を照射（露光）し、露光後の組成物層に現像液を接触させて着色パターンまたは着色塗膜を形成（現像）する工程を含む。この現像後、しばしば、着色パターンを加熱するポストベークが行われる。 Examples of the method for forming the color filter from the color curable resin composition include a photolithography method and a method using an inkjet device. In the photolithography method, a color curable resin composition is usually applied onto a substrate, and volatile components such as a solvent are removed by heat drying (prebaking) and / or vacuum drying to form a composition layer, and the composition is formed. It includes a step of irradiating (exposing) light on the layer and bringing a developing solution into contact with the exposed composition layer to form (develop) a colored pattern or a colored coating film. After this development, post-baking is often performed to heat the coloring pattern.
　従来の着色硬化性樹脂組成物では、ポストベークによって着色パターンまたは着色塗膜の厚さが大幅に減少することがあった。本発明はこのような事情に着目してなされたものであって、その目的は、加熱（特にポストベーク）による着色パターンまたは着色塗膜の厚さの減少を抑制し得る着色硬化性樹脂組成物を提供することにある。 In the conventional colored curable resin composition, the thickness of the colored pattern or the colored coating film may be significantly reduced by post-baking. The present invention has been made in view of such circumstances, and an object of the present invention is a coloring curable resin composition capable of suppressing a decrease in a coloring pattern or a thickness of a coloring coating film due to heating (particularly post-baking). Is to provide.
　上記目的を達成し得る本発明は、以下の通りである。
　［１］　着色剤（Ａ）、樹脂（Ｂ）、重合性化合物（Ｃ）および重合開始剤（Ｄ）を含む着色硬化性樹脂組成物であって、
　着色硬化性樹脂組成物が、さらにフェノール系酸化防止剤（Ｅ）を含み、
　樹脂（Ｂ）が、式（１ｂ）： The present invention that can achieve the above object is as follows.
[1] A color curable resin composition containing a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).
The color curable resin composition further contains a phenolic antioxidant (E).
The resin (B) is the formula (1b):
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
［式（１ｂ）中、Ｒ１Ｂは、水素原子またはメチル基を表し、
　Ｒ２Ｂ～Ｒ４Ｂは、それぞれ独立に、水素原子、炭素数１～６のアルキル基または炭素数１～６のアルコキシ基を表し、
　ｎは、１～１０の整数を表し、および
　＊は、結合位置を表し、
　但し、Ｒ２Ｂ～Ｒ４Ｂの少なくとも一つは、炭素数１～６のアルコキシ基である。］
で表される構成単位（ｂ１－１）を含む樹脂（Ｂ１）を含む着色硬化性樹脂組成物。
　［２］　樹脂（Ｂ１）が、構成単位（ｂ１－１）、酸性基を有する重合性不飽和化合物に由来する構成単位（ｂ１－２）および他の構成単位（ｂ１－３）を含む共重合体であり、且つ共重合体中の全構成単位の合計を１００モル％としたときの構成単位（ｂ１－１）の量が、１～５０モル％である前記［１］に記載の着色硬化性樹脂組成物。
　［３］　樹脂（Ｂ１）の重量平均分子量が１，０００～５０，０００である前記［１］または［２］に記載の着色硬化性樹脂組成物。
　［４］　樹脂（Ｂ１）の含有量が、重合性化合物（Ｃ）１００重量部に対して５～４００重量部である前記［１］～［３］のいずれか一つに記載の着色硬化性樹脂組成物。
　［５］　フェノール系酸化防止剤（Ｅ）の含有量が、重合性化合物（Ｃ）１００重量部に対して０．１～２５重量部である前記［１］～［４］のいずれか一つに記載の着色硬化性樹脂組成物。
　［６］　着色剤（Ａ）が、染料（Ａ１）および顔料（Ａ２）を含む前記［１］～［５］のいずれか一つに記載の着色硬化性樹脂組成物。
　［７］　重合性化合物（Ｃ）が、ラジカル重合性化合物であり、且つ重合開始剤（Ｄ）が、光ラジカル重合開始剤である前記［１］～［６］のいずれか一つに記載の着色硬化性樹脂組成物。
　［８］　着色剤（Ａ）が、式（Ａ３－１）： [In formula (1b), R 1B represents a hydrogen atom or a methyl group.
R 2B to R 4B independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
n represents an integer from 1 to 10, and * represents the bond position.
However, at least one of R 2B to R 4B is an alkoxy group having 1 to 6 carbon atoms. ]
A colored curable resin composition containing a resin (B1) containing a structural unit (b1-1) represented by.
[2] The resin (B1) contains a structural unit (b1-1), a structural unit (b1-2) derived from a polymerizable unsaturated compound having an acidic group, and another structural unit (b1-3). The color curing according to the above [1], wherein the amount of the structural units (b1-1) is 1 to 50 mol% when the total of all the structural units in the copolymer is 100 mol%. Sex resin composition.
[3] The colored curable resin composition according to the above [1] or [2], wherein the resin (B1) has a weight average molecular weight of 1,000 to 50,000.
[4] The color curability according to any one of the above [1] to [3], wherein the content of the resin (B1) is 5 to 400 parts by weight with respect to 100 parts by weight of the polymerizable compound (C). Resin composition.
[5] Any one of the above [1] to [4], wherein the content of the phenolic antioxidant (E) is 0.1 to 25 parts by weight with respect to 100 parts by weight of the polymerizable compound (C). The colored curable resin composition according to.
[6] The color curable resin composition according to any one of the above [1] to [5], wherein the colorant (A) contains a dye (A1) and a pigment (A2).
[7] The above-mentioned [1] to [6], wherein the polymerizable compound (C) is a radically polymerizable compound and the polymerization initiator (D) is a photoradical polymerization initiator. Color curable resin composition.
[8] The colorant (A) has the formula (A3-1):
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
［式（Ａ３－１）中、Ｒ４１ａおよびＲ４２ａは、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１～２０の飽和炭化水素基、置換基を有していてもよい炭素数６～１４の芳香族炭化水素基、または置換基を有していてもよい炭素数７～３０のアラルキル基を表すか、或いはＲ４１ａとＲ４２ａとが結合して、それらが結合する窒素原子と共に３～１０員の含窒素複素環を形成し、
　Ｒ４３ａおよびＲ４４ａは、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１～２０の飽和炭化水素基、置換基を有していてもよい炭素数６～１４の芳香族炭化水素基、または置換基を有していてもよい炭素数７～３０のアラルキル基を表すか、或いはＲ４３ａとＲ４４ａとが結合してそれらが結合する窒素原子と共に３～１０員の含窒素複素環を形成し、
　Ｒ４７ａ～Ｒ５４ａは、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、ヒドロキシ基、－ＳＯ３ －、－ＳＯ２－Ｎ－－ＳＯ２－Ｒｆ、または置換基を有していてもよい炭素数１～８のアルキル基を表し、
　Ｒｆは、炭素数１～１２のフルオロアルキル基を表し、
　環Ｔ１ａは、置換基を有していてもよい炭素数６～１４の芳香族炭化水素環または置換基を有していてもよい５～１０員の芳香族複素環を表し、
　前記炭素数１～２０の飽和炭化水素基が有していてもよい置換基は、ハロゲン原子、ヒドロキシ基、ホルミル基およびアミノ基からなる群から選ばれる少なくとも一つであり、
　前記炭素数６～１４の芳香族炭化水素基が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、－ＳＯ３ －、－ＳＯ２－Ｎ－－ＳＯ２－Ｒｆ、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つであり、
　前記炭素数７～３０のアラルキル基が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、－ＳＯ３ －、－ＳＯ２－Ｎ－－ＳＯ２－Ｒｆ、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つであり、
　前記炭素数６～１４の芳香族炭化水素環が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、－ＳＯ３ －、－ＳＯ２－Ｎ－－ＳＯ２－Ｒｆ、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つであり、
　前記５～１０員の芳香族複素環が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、－ＳＯ３ －、－ＳＯ２－Ｎ－－ＳＯ２－Ｒｆ、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つであり、
　前記炭素数１～８のアルキル基が有していてもよい置換基は、ハロゲン原子、ヒドロキシ基、ホルミル基およびアミノ基からなる群から選ばれる少なくとも一つであり、
　前記炭素数１～２０の飽和炭化水素基が炭素数２～２０の飽和炭化水素基である場合、前記飽和炭化水素基に含まれる－ＣＨ２－は、－Ｏ－または－ＣＯ－に置き換わっていてもよく、
　前記炭素数１～８のアルキル基が炭素数２～８のアルキル基である場合、前記アルキル基に含まれる－ＣＨ２－は、－Ｏ－または－ＣＯ－に置き換わっていてもよく、
　ｒは、１以上の整数を表し、
　Ｍｒ＋は、水素イオン、ｒ価の金属イオンまたはＮ＋（Ｒ５５ａ）４を表し、四つのＲ５５ａは同一でも、異なっていてもよく、
　Ｒ５５ａは、水素原子、炭素数１～２０の飽和炭化水素基または炭素数７～１０のアラルキル基を表し、
　ｋは、式（Ａ３－１ａ）： [In the formula (A3-1), R 41a and R 42a each independently have a hydrogen atom and a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and a substituent. It represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R 41a and R 42a are bonded to each other. Form a 3- to 10-membered nitrogen-containing heterocycle with the nitrogen atom to which
R 43a and R 44a each independently have a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and 6 to 14 carbon atoms which may have a substituent. It represents an aromatic hydrocarbon group, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or 3 to 10 members together with a nitrogen atom to which R 43a and R 44a are bonded and bonded to each other. Forming a nitrogen-containing heterocycle of
R 47a ~ R 54a are each independently a hydrogen atom, a halogen atom, a nitro group, hydroxy group, -SO 3 -, -SO 2 -N - have -SO 2 -R f or a substituent, Represents a good alkyl group with 1 to 8 carbon atoms
R f represents a fluoroalkyl group having 1 to 12 carbon atoms.
Ring T 1a represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms which may have a substituent or a 5 to 10 member aromatic heterocycle which may have a substituent.
The substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
The aromatic hydrocarbon group substituents which may be possessed by the carbon number of 6 to 14, a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - -SO 2 - R f , and at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have a substituent.
Substituents which may be the aralkyl group have the carbon number of 7 to 30, a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - -SO 2 -R f, And at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have substituents.
Aromatic hydrocarbon ring substituent that have the carbon number of 6 to 14, a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - -SO 2 - R f , and at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have a substituent.
Wherein said 5 to 10-membered aromatic heterocyclic ring substituent which may have of a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - -SO 2 -R f , And at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have substituents.
The substituent which the alkyl group having 1 to 8 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
When the saturated hydrocarbon group having 1 to 20 carbon atoms is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH 2- contained in the saturated hydrocarbon group is replaced with -O- or -CO-. May be
When the alkyl group having 1 to 8 carbon atoms is an alkyl group having 2 to 8 carbon atoms, -CH 2- contained in the alkyl group may be replaced with -O- or -CO-.
r represents an integer of 1 or more
Mr + represents a hydrogen ion, an r-valent metal ion or N + (R 55a ) 4 , and the four R 55a may be the same or different.
R 55a represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.
k is the formula (A3-1a):
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
［式（Ａ３－１ａ）中、環Ｔ１ａ、Ｒ４１ａ～Ｒ４４ａおよびＲ４７ａ～Ｒ５４ａは、それぞれ、上記と同義である。］
で表されるアニオンが有する－ＳＯ３ －および－ＳＯ２－Ｎ－－ＳＯ２－Ｒｆの個数の合計を表し、且つ２以上の整数であり、
　ｒが２以上の整数である場合、式（Ａ３－１ａ）で表される複数のアニオンは、同一でも、異なっていてもよく、並びに
　ｋ－１が２以上の整数である場合、複数のＭｒ＋は、同一でも、異なっていてもよい。］
で表される化合物、および
　式（Ａ３－２）： [In the formula (A3-1a), the rings T 1a , R 41a to R 44a and R 47a to R 54a are synonymous with the above, respectively. ]
In -SO 3 anion has represented - and -SO 2 -N - represents the total number of -SO 2 -R f, a and an integer of 2 or more,
When r is an integer of 2 or more, the plurality of anions represented by the formula (A3-1a) may be the same or different, and when k-1 is an integer of 2 or more, a plurality of Ms. r + may be the same or different. ]
The compound represented by, and the formula (A3-2):
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
［式（Ａ３－２）中、Ｒ４１ｂおよびＲ４２ｂは、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１～２０の飽和炭化水素基、置換基を有していてもよい炭素数６～
１４の芳香族炭化水素基、または置換基を有していてもよい炭素数７～３０のアラルキル基を表すか、或いはＲ４１ｂとＲ４２ｂとが結合して、それらが結合する窒素原子と共に３～１０員の含窒素複素環を形成し、
　Ｒ４３ｂおよびＲ４４ｂは、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１～２０の飽和炭化水素基、置換基を有していてもよい炭素数６～１４の芳香族炭化水素基、または置換基を有していてもよい炭素数７～３０のアラルキル基を表すか、或いはＲ４３ｂとＲ４４ｂとが結合してそれらが結合する窒素原子と共に３～１０員の含窒素複素環を形成し、
　Ｒ４７ｂ～Ｒ５４ｂは、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、ヒドロキシ基、または置換基を有していてもよい炭素数１～８のアルキル基を表し、
　環Ｔ１ｂは、置換基を有していてもよい炭素数６～１４の芳香族炭化水素環または置換基を有していてもよい５～１０員の芳香族複素環を表し、
　前記炭素数１～２０の飽和炭化水素基が有していてもよい置換基は、ハロゲン原子、ヒドロキシ基、ホルミル基およびアミノ基からなる群から選ばれる少なくとも一つであり、
　前記炭素数６～１４の芳香族炭化水素基が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つであり、
　前記炭素数７～３０のアラルキル基が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つであり、
　前記炭素数６～１４の芳香族炭化水素環が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つであり、
　前記５～１０員の芳香族複素環が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つであり、
　前記炭素数１～８のアルキル基が有していてもよい置換基は、ハロゲン原子、ヒドロキシ基、ホルミル基およびアミノ基からなる群から選ばれる少なくとも一つであり、
　前記炭素数１～２０の飽和炭化水素基が炭素数２～２０の飽和炭化水素基である場合、前記飽和炭化水素基に含まれる－ＣＨ２－は、－Ｏ－または－ＣＯ－に置き換わっていてもよく、
　前記炭素数１～８のアルキル基が炭素数２～８のアルキル基である場合、前記アルキル基に含まれる－ＣＨ２－は、－Ｏ－または－ＣＯ－に置き換わっていてもよく、
　ｍは、１以上の整数を表し、
　［Ｙ］ｍ－は、ｍ価のアニオンを表し、並びに
　ｍが２以上の整数である場合、式（Ａ３－２ｃ）： [In the formula (A3-2), R 41b and R 42b each independently have a hydrogen atom and a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent which may have a substituent. May have 6 to carbon atoms
Represents an aromatic hydrocarbon group of 14 or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R 41b and R 42b are bonded and 3 together with the nitrogen atom to which they are bonded. Forming a nitrogen-containing heterocycle of ~ 10 members,
R 43b and R 44b independently have a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and 6 to 14 carbon atoms which may have a substituent. It represents an aromatic hydrocarbon group, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or 3 to 10 members together with a nitrogen atom to which R 43b and R 44b are bonded and bonded to each other. Forming a nitrogen-containing heterocycle of
R 47b to R 54b each independently represent an alkyl group having 1 to 8 carbon atoms which may have a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or a substituent.
Ring T 1b represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms which may have a substituent or a 5 to 10 member aromatic heterocycle which may have a substituent.
The substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
The substituents that the aromatic hydrocarbon group having 6 to 14 carbon atoms may have may have a halogen atom, a nitro group, a hydroxy group, a formyl group, and a substituent having 1 to 8 carbon atoms. At least one selected from the group consisting of alkyl groups of
The substituents that the aralkyl group having 7 to 30 carbon atoms may have are a halogen atom, a nitro group, a hydroxy group, a formyl group, and an alkyl group having 1 to 8 carbon atoms that may have a substituent. At least one selected from the group consisting of
The substituents that the aromatic hydrocarbon ring having 6 to 14 carbon atoms may have may have a halogen atom, a nitro group, a hydroxy group, a formyl group, and a substituent having 1 to 8 carbon atoms. At least one selected from the group consisting of alkyl groups of
Substituents that the 5- to 10-membered aromatic heterocycle may have are halogen atoms, nitro groups, hydroxy groups, formyl groups, and alkyl having 1 to 8 carbon atoms that may have substituents. At least one selected from the group of groups,
The substituent which the alkyl group having 1 to 8 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
When the saturated hydrocarbon group having 1 to 20 carbon atoms is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH 2- contained in the saturated hydrocarbon group is replaced with -O- or -CO-. May be
When the alkyl group having 1 to 8 carbon atoms is an alkyl group having 2 to 8 carbon atoms, -CH 2- contained in the alkyl group may be replaced with -O- or -CO-.
m represents an integer of 1 or more
[Y] m- represents an m-valent anion, and when m is an integer of 2 or more, the formula (A3-2c):
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
［式（Ａ３－２ｃ）中、環Ｔ１ｂ、Ｒ４１ｂ～Ｒ４４ｂおよびＲ４７ｂ～Ｒ５４ｂは、それぞれ、上記と同義である。］
で表される複数のカチオンは、同一でも、異なっていてもよい。］
で表される化合物からなる群から選ばれる少なくとも一つの化合物（Ａ３）を含む前記［１］～［７］のいずれか一つに記載の着色硬化性樹脂組成物。
　［９］　着色剤（Ａ）が、化合物（Ａ３）とは異なる染料（Ａ１）を含む前記［８］に記載の着色硬化性樹脂組成物。 [In the formula (A3-2c), rings T 1b , R 41b to R 44b and R 47b to R 54b are synonymous with the above, respectively. ]
The plurality of cations represented by may be the same or different. ]
The colored curable resin composition according to any one of the above [1] to [7], which comprises at least one compound (A3) selected from the group consisting of the compounds represented by.
[9] The color curable resin composition according to the above [8], wherein the colorant (A) contains a dye (A1) different from the compound (A3).
　本発明の着色硬化性樹脂組成物を用いれば、加熱（特にポストベーク）による着色パターンまたは着色塗膜の厚さの減少を抑制することができる。 By using the colored curable resin composition of the present invention, it is possible to suppress a decrease in the thickness of the colored pattern or the colored coating film due to heating (particularly post-baking).
　本発明の着色硬化性樹脂組成物は、着色剤（Ａ）、樹脂（Ｂ）、重合性化合物（Ｃ）、重合開始剤（Ｄ）およびフェノール系酸化防止剤（Ｅ）を含む。さらに、樹脂（Ｂ）は、上記式（１ｂ）で表される構成単位（ｂ１－１）を含む樹脂（Ｂ１）を含む。以下、本発明の着色硬化性樹脂組成物の各成分を順に説明する。 The color curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a phenolic antioxidant (E). Further, the resin (B) includes a resin (B1) containing a structural unit (b1-1) represented by the above formula (1b). Hereinafter, each component of the colored curable resin composition of the present invention will be described in order.
　本明細書において説明する各成分および各成分を製造するための原料は、特に断りのない限り、いずれも１種のみを使用してもよく、２種以上を併用してもよい。 Unless otherwise specified, only one type of each component and the raw material for producing each component described in the present specification may be used, or two or more types may be used in combination.
＜着色剤（Ａ）＞
　着色剤（Ａ）は、溶剤に可溶な染料（Ａ１）と、溶剤に不溶な顔料（Ａ２）に分類される。本発明の一態様では、着色剤（Ａ）は、染料（Ａ１）および顔料（Ａ２）の両方を含む。 <Colorant (A)>
The colorant (A) is classified into a solvent-soluble dye (A1) and a solvent-insoluble pigment (A2). In one aspect of the invention, the colorant (A) comprises both the dye (A1) and the pigment (A2).
　染料（Ａ１）は、好ましくはキサンテン染料、トリアリールメタン染料およびクマリン染料からなる群から選ばれる少なくとも一つの染料を含む。前記群から選ばれる少なくとも一つの染料を使用する場合、その合計量は、染料（Ａ１）全体に対して、好ましくは１重量％以上、１００重量％以下であり、より好ましくは２重量％以上、１００重量％以下であり、さらに好ましくは５重量％以上、１００重量％以下である。 The dye (A1) preferably contains at least one dye selected from the group consisting of xanthene dyes, triarylmethane dyes and coumarin dyes. When at least one dye selected from the above group is used, the total amount thereof is preferably 1% by weight or more, 100% by weight or less, and more preferably 2% by weight or more, based on the entire dye (A1). It is 100% by weight or less, more preferably 5% by weight or more and 100% by weight or less.
　染料（Ａ１）は、より好ましくはキサンテン染料を含む。キサンテン染料を使用する場合、その含有量は、染料（Ａ１）全体に対して、好ましくは１重量％以上、１００重量％以下であり、より好ましくは２重量％以上、１００重量％以下であり、さらに好ましくは５重量％以上、１００重量％以下であり、最も好ましくは１００重量％である。即ち、染料（Ａ１）は、最も好ましくはキサンテン染料からなる。 The dye (A1) more preferably contains a xanthene dye. When a xanthene dye is used, its content is preferably 1% by weight or more and 100% by weight or less, more preferably 2% by weight or more and 100% by weight or less, based on the entire dye (A1). More preferably, it is 5% by weight or more, 100% by weight or less, and most preferably 100% by weight. That is, the dye (A1) is most preferably composed of a xanthene dye.
　キサンテン染料は、分子内にキサンテン骨格を有する化合物を含む染料である。キサンテン染料としては、例えば、Ｃ．Ｉ．アシッドレッド５１（以下、Ｃ．Ｉ．アシッドレッドの記載を省略し、番号のみの記載とする。他も同様である。）、５２、８７、９２、９４、２８９、３８８、Ｃ．Ｉ．アシッドバイオレット９、３０、１０２、Ｃ．Ｉ．ベーシックレッド１（ローダミン６Ｇ）、２、３、４、８、Ｃ．Ｉ．ベーシックレッド１０、１１、Ｃ．Ｉ．ベーシックバイオレット１０（ローダミンＢ）、１１、Ｃ．Ｉ．ソルベントレッド２１８、Ｃ．Ｉ．モーダントレッド２７、Ｃ．Ｉ．リアクティブレッド３６（ローズベンガルＢ）、スルホローダミンＧ、特開２０１０－３２９９９号公報に記載のキサンテン染料および特許第４４９２７６０号公報に記載のキサンテン染料等が挙げられる。キサンテン染料としては、有機溶剤に溶解するものが好ましい。 The xanthene dye is a dye containing a compound having a xanthene skeleton in the molecule. Examples of the xanthene dye include C.I. I. Acid Red 51 (hereinafter, the description of CI Acid Red is omitted and only the number is described. The same applies to the others), 52, 87, 92, 94, 289, 388, C.I. I. Acid Violet 9, 30, 102, C.I. I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. I. Basic Red 10, 11, C.I. I. Basic Violet 10 (Rhodamine B), 11, C.I. I. Solvent Red 218, C.I. I. Modant Red 27, C.I. I. Examples thereof include reactive red 36 (rose bengal B), sulforhodamine G, xanthene dyes described in JP-A-2010-32999, and xanthene dyes described in Japanese Patent No. 4492760. The xanthene dye is preferably one that dissolves in an organic solvent.
　好ましいキサンテン染料としては、式（１ａ）で表される化合物（以下「化合物（１ａ）」と記載することがある）が挙げられる。化合物（１ａ）は、その互変異性体であってもよい。化合物（１ａ）を用いる場合、その含有量は、キサンテン染料全体に対して、好ましくは５０重量％以上、より好ましくは７０重量％以上、さらに好ましくは９０重量％以上である。特に、キサンテン染料として、化合物（１ａ）のみを使用することが好ましい。 Preferred xanthene dyes include compounds represented by the formula (1a) (hereinafter sometimes referred to as "compound (1a)"). Compound (1a) may be a tautomer thereof. When compound (1a) is used, its content is preferably 50% by weight or more, more preferably 70% by weight or more, still more preferably 90% by weight or more, based on the total amount of the xanthene dye. In particular, it is preferable to use only compound (1a) as the xanthene dye.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
［式（１ａ）中、Ｒ１～Ｒ４は、それぞれ独立に、水素原子、置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基、置換基を有していてもよい炭素数６～１０の１価の芳香族炭化水素基または＊－Ｒ１２－Ｓｉ（Ｒ１３）３で表される基（前記式中、＊は窒素原子との結合位置を表し）を表し、前記飽和炭化水素基に含まれる－ＣＨ２－は、－Ｏ－、－ＣＯ－または－ＮＲ１１－で置き換わっていてもよく、
　Ｒ１およびＲ２は、一緒になって窒素原子を含む環を形成してもよく、Ｒ３およびＲ４は、一緒になって窒素原子を含む環を形成してもよく、
　Ｒ５は、－ＯＨ、－ＳＯ３ －、－ＳＯ３Ｈ、－ＳＯ３ －Ｚ＋、－ＣＯ２Ｈ、－ＣＯ２ －Ｚ＋、－ＣＯ２Ｒ８、－ＳＯ３Ｒ８または－ＳＯ２ＮＲ９Ｒ１０を表し、
　Ｒ６およびＲ７は、それぞれ独立に、水素原子または炭素数１～６のアルキル基を表し、
　ｍは、０～５の整数を表し、ｍが２以上のとき、複数のＲ５は同一でも異なってもよく、
　ａは、０または１の整数を表し、
　Ｘは、ハロゲン原子を表し、
　Ｚ＋は、Ｎ＋（Ｒ１１）４、Ｎａ＋またはＫ＋を表し、四つのＲ１１は同一でも異なってもよく、
　Ｒ８は、ハロゲン原子で置換されていてもよい炭素数１～２０の１価の飽和炭化水素基を表し、
　Ｒ９およびＲ１０は、それぞれ独立に、水素原子または置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基を表し、前記飽和脂肪族炭化水素基に含まれる－ＣＨ２－は、－Ｏ－、－ＣＯ－、－ＮＨ－または－ＮＲ８－で置き換っていてもよく、Ｒ９およびＲ１０は、互いに結合して窒素原子を含んだ３～１０員環の複素環を形成していてもよく、
　Ｒ１１は、水素原子、炭素数１～２０の１価の飽和炭化水素基または炭素数７～１０のアラルキル基を表し、
　Ｒ１２は、炭素数１～１０のアルカンジイル基を表し、前記アルカンジイル基に含まれる－ＣＨ２－は、－Ｏ－、－ＣＯ－、－ＮＲ８－、－ＯＣＯ－、－ＣＯＯ－、－ＯＣＯＮＨ－、－ＣＯＮＨ－または－ＮＨＣＯ－で置換されていてもよく、並びに
　Ｒ１３は、水素原子、ヒドロキシ基、炭素数１～４のアルキル基または炭素数１～４のアルコキシ基を表し、および複数のＲ１３は、それぞれ同一でも異なってもよく、
　但し、式（１ａ）中にイオンの形態の－ＳＯ３ －が存在する場合、その数は１個である。］ [In the formula (1a), R 1 to R 4 each independently have a hydrogen atom and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and a substituent. A monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a group represented by * -R 12- Si (R 13 ) 3 (in the above formula, * represents a bond position with a nitrogen atom). the stands, the -CH 2 - contained in the saturated hydrocarbon group - is, -O -, - CO- or -NR 11 - may be replaced by,
R 1 and R 2 may be combined to form a ring containing a nitrogen atom, and R 3 and R 4 may be combined to form a ring containing a nitrogen atom.
R 5 is, -OH, -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO Represents 2 NR 9 R 10
R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer from 0 to 5, and when m is 2 or more, a plurality of R 5s may be the same or different.
a represents an integer of 0 or 1 and represents
X represents a halogen atom
Z + stands for N + (R 11 ) 4 , Na + or K + , and the four R 11s may be the same or different.
R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom.
R 9 and R 10 each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a substituent, and are contained in the saturated aliphatic hydrocarbon group. CH 2 - is, -O -, - CO -, - NH- or -NR 8 - may have I placed conversion in, R 9 and R 10, 3-10 membered containing nitrogen atoms bonded to each other It may form a heterocycle of rings,
R 11 represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.
R 12 represents an alkanediyl group having 1 to 10 carbon atoms, -CH 2 contained in the alkanediyl group - is, -O -, - CO -, - NR 8 -, - OCO -, - COO-, -OCONH -, - CONH- or -NHCO- may be substituted by, and R 13 represents a hydrogen atom, a hydroxy group, an alkyl group or an alkoxy group having 1 to 4 carbon atoms having 1 to 4 carbon atoms, And the plurality of R 13s may be the same or different, respectively.
However, -SO 3 ions in the form in formula (1a) - if there is, the number is one. ]
　Ｒ１～Ｒ４における置換基を有していてもよい炭素数６～１０の１価の芳香族炭化水素基としては、例えば、フェニル基、トリル基、キシリル基、メシチル基、プロピルフェニル基およびブチルフェニル基等が挙げられる。 Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent in R 1 to R 4 include a phenyl group, a tolyl group, a xsilyl group, a mesityl group, a propylphenyl group and the like. Examples include a butylphenyl group.
　前記芳香族炭化水素基が有していてもよい置換基としては、ハロゲン原子、－Ｒ８、－ＯＨ、－ＯＲ８、－ＳＯ３ －、－ＳＯ３Ｈ、－ＳＯ３ －Ｚ＋、－ＣＯ２Ｈ、－ＣＯ２Ｒ８、－ＳＲ８、－ＳＯ２Ｒ８、－ＳＯ３Ｒ８または－ＳＯ２ＮＲ９Ｒ１０が挙げられる。これらの中でも、－ＳＯ３ －、－ＳＯ３Ｈ、－ＳＯ３ －Ｚ＋および－ＳＯ２ＮＲ９Ｒ１０が好ましく、－ＳＯ３ －Ｚ＋および－ＳＯ２ＮＲ９Ｒ１０がより好ましい。この場合の－ＳＯ３ －Ｚ＋としては、－ＳＯ３ －Ｎ＋（Ｒ１１）４が好ましい。 The aromatic hydrocarbon group substituent which may have a halogen atom, -R 8, -OH, -OR 8 , -SO 3 -, -SO 3 H, -SO 3 - Z +, - Examples thereof include CO 2 H, -CO 2 R 8 , -SR 8 , -SO 2 R 8 , -SO 3 R 8 or -SO 2 NR 9 R 10 . Among these, -SO 3 -, -SO 3 H , -SO 3 - Z + and -SO 2 NR 9 R 10 is preferably, -SO 3 - Z + and -SO 2 NR 9 R 10 is more preferred. In this case, as -SO 3 - Z + , -SO 3 - N + (R 11 ) 4 is preferable.
　Ｒ１～Ｒ４およびＲ８～Ｒ１１における炭素数１～２０の１価の飽和炭化水素基は、直鎖状、分岐鎖状または環状のいずれでもよい。その例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、ヘキサデシル基、イコシル基、イソプロピル基、イソブチル基、イソペンチル基、ネオペンチル基、２－エチルヘキシル基等の炭素数１～２０のアルキル基；シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、トリシクロデシル基等の炭素数３～２０の脂環式飽和炭化水素基が挙げられる。 The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 1 to R 4 and R 8 to R 11 may be linear, branched chain or cyclic. Examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, icosyl group, isopropyl group, isobutyl group, Alkyl group having 1 to 20 carbon atoms such as isopentyl group, neopentyl group and 2-ethylhexyl group; 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group. The alicyclic saturated hydrocarbon group of is mentioned.
　Ｒ１～Ｒ４における飽和炭化水素基が有していてもよい置換基としては、例えば、炭素数６～１０の芳香族炭化水素基、ハロゲン原子およびカルボキシ基が挙げられる。
　Ｒ９およびＲ１０における飽和炭化水素基が有していてもよい置換基としては、例えば、ヒドロキシ基およびハロゲン原子が挙げられる。 Substituents that the saturated hydrocarbon groups in R 1 to R 4 may have include, for example, aromatic hydrocarbon groups having 6 to 10 carbon atoms, halogen atoms and carboxy groups.
Substituents that the saturated hydrocarbon groups in R 9 and R 10 may have include, for example, hydroxy groups and halogen atoms.
　Ｒ１およびＲ２が一緒になって形成する環、並びにＲ３およびＲ４が一緒になって形成する環としては、例えば、以下のものが挙げられる。 Examples of the ring formed by R 1 and R 2 together and the ring formed by R 3 and R 4 together include the following.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　－ＯＲ８としては、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基、２－エチルヘキシルオキシ基およびイコシルオキシ基等が挙げられる。 Examples of -OR 8 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group and an icosyloxy group.
　－ＣＯ２Ｒ８としては、例えば、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、ｔｅｒｔ－ブトキシカルボニル基、ヘキシルオキシカルボニル基およびイコシルオキシカルボニル基等が挙げられる。 Examples of -CO 2 R 8 include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, an icosyloxycarbonyl group and the like.
　－ＳＲ８としては、例えば、メチルスルファニル基、エチルスルファニル基、ブチルスルファニル基、ヘキシルスルファニル基、デシルスルファニル基およびイコシルスルファニル基等が挙げられる。
　－ＳＯ２Ｒ８としては、例えば、メチルスルホニル基、エチルスルホニル基、ブチルスルホニル基、ヘキシルスルホニル基、デシルスルホニル基およびイコシルスルホニル基等が挙げられる。
　－ＳＯ３Ｒ８としては、例えば、メトキシスルホニル基、エトキシスルホニル基、プロポキシスルホニル基、ｔｅｒｔ－ブトキシスルホニル基、ヘキシルオキシスルホニル基およびイコシルオキシスルホニル基等が挙げられる。 Examples of the -SR 8 include a methylsulfanil group, an ethylsulfanil group, a butylsulfanil group, a hexylsulfanil group, a decylsulfanil group, an icosylsulfanil group and the like.
-SO 2 R 8 includes, for example, a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, an icosylsulfonyl group and the like.
Examples of the -SO 3 R 8 include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group and an icosyloxysulfonyl group.
　－ＳＯ２ＮＲ９Ｒ１０としては、例えば、以下のものが挙げられる：
スルファモイル基；
Ｎ－メチルスルファモイル基、Ｎ－エチルスルファモイル基、Ｎ－プロピルスルファモイル基、Ｎ－イソプロピルスルファモイル基、Ｎ－ブチルスルファモイル基、Ｎ－イソブチルスルファモイル基、Ｎ－ｓｅｃ－ブチルスルファモイル基、Ｎ－ｔｅｒｔ－ブチルスルファモイル基、Ｎ－ペンチルスルファモイル基、Ｎ－（１－エチルプロピル）スルファモイル基、Ｎ－（１，１－ジメチルプロピル）スルファモイル基、Ｎ－（１，２－ジメチルプロピル）スルファモイル基、Ｎ－（２，２－ジメチルプロピル）スルファモイル基、Ｎ－（１－メチルブチル）スルファモイル基、Ｎ－（２－メチルブチル）スルファモイル基、Ｎ－（３－メチルブチル）スルファモイル基、Ｎ－シクロペンチルスルファモイル基、Ｎ－ヘキシルスルファモイル基、Ｎ－（１，３－ジメチルブチル）スルファモイル基、Ｎ－（３，３－ジメチルブチル）スルファモイル基、Ｎ－ヘプチルスルファモイル基、Ｎ－（１－メチルヘキシル）スルファモイル基、Ｎ－（１，４－ジメチルペンチル）スルファモイル基、Ｎ－オクチルスルファモイル基、Ｎ－（２－エチルヘキシル）スルファモイル基、Ｎ－（１，５－ジメチル）ヘキシルスルファモイル基、Ｎ－（１，１，２，２－テトラメチルブチル）スルファモイル基等のＮ－１置換スルファモイル基；
Ｎ，Ｎ－ジメチルスルファモイル基、Ｎ，Ｎ－エチルメチルスルファモイル基、Ｎ，Ｎ－ジエチルスルファモイル基、Ｎ，Ｎ－プロピルメチルスルファモイル基、Ｎ，Ｎ－イソプロピルメチルスルファモイル基、Ｎ，Ｎ－ｔｅｒｔ－ブチルメチルスルファモイル基、Ｎ，Ｎ－ブチルエチルスルファモイル基、Ｎ，Ｎ－ビス（１－メチルプロピル）スルファモイル基、Ｎ，Ｎ－ヘプチルメチルスルファモイル基等のＮ，Ｎ－２置換スルファモイル基等。 -SO 2 NR 9 R 10 includes, for example:
Sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-Butyl sulfamoyl group, N-tert-Butyl sulfamoyl group, N-pentyl sulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3) -Methylbutyl) sulfamoyl group, N-cyclopentyl sulfamoyl group, N-hexyl sulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N- Heptyl sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octyl sulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- N-1 substituted sulfamoyl groups such as (1,5-dimethyl) hexyl sulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group;
N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfa Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl N, N-2-substituted sulfamoyl groups such as groups.
　Ｒ５は、好ましくは－ＣＯ２Ｈ、－ＣＯ２ －Ｚ＋、－ＣＯ２Ｒ８、－ＳＯ３ －、－ＳＯ３ －Ｚ＋、－ＳＯ３ＨまたはＳＯ２ＮＨＲ９であり、より好ましくはＳＯ３ －、－ＳＯ３ －Ｚ＋、－ＳＯ３ＨまたはＳＯ２ＮＨＲ９である。
　ｍは、好ましくは１～４であり、より好ましくは１または２である。 R 5 is preferably -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 -, -SO 3 - Z +, a -SO 3 H or SO 2 NHR 9, more preferably is SO 3 -, -SO 3 - Z +, a -SO 3 H or SO 2 NHR 9.
m is preferably 1 to 4, more preferably 1 or 2.
　Ｒ６およびＲ７における炭素数１～６のアルキル基としては、例えば、上記で挙げたアルキル基のうち、炭素数１～６のものが挙げられる。 Examples of the alkyl group having 1 to 6 carbon atoms in R 6 and R 7 include those having 1 to 6 carbon atoms among the alkyl groups listed above.
　Ｒ１１における炭素数７～１０のアラルキル基としては、例えば、ベンジル基、フェニルエチル基、フェニルブチル基等が挙げられる。 Examples of the aralkyl group having 7 to 10 carbon atoms in R 11 include a benzyl group, a phenylethyl group, a phenylbutyl group and the like.
　Ｒ１２における炭素数１～１０のアルカンジイル基としては、例えば、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、イソプロピレン基、イソブチレン基、２－メチルトリメチレン基、イソペンチレン基、イソヘキシレン基、イソオクチレン基、２－エチルへキシレン基等が挙げられる。これらのなかでは、炭素数１～６のアルカンジイル基が好ましく、炭素数１～４のアルカンジイル基がより好ましい。 The alkanediyl group having 1 to 10 carbon atoms in R 12, for example, methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, isopropylene group, isobutylene group, 2-methyltrimethylene Examples thereof include a group, an isopentylene group, an isohexylene group, an isooctylene group, a 2-ethylhexylene group and the like. Among these, an alkanediyl group having 1 to 6 carbon atoms is preferable, and an alkanediyl group having 1 to 4 carbon atoms is more preferable.
　Ｒ１３における炭素数１～４のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基が挙げられる。
　Ｒ１３における炭素数１～４のアルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、ｔ－ブトキシ基等が挙げられる。
　Ｒ１３としては、メチル基、エチル基、メトキシ基、エトキシ基が好ましく、メトキシ基またはエトキシ基がより好ましい。 Examples of the alkyl group having 1 to 4 carbon atoms in R 13 include a methyl group, an ethyl group, a propyl group and a butyl group.
Examples of the alkoxy group having 1 to 4 carbon atoms in R 13 include a methoxy group, an ethoxy group, a propoxy group, a t-butoxy group and the like.
The R 13, a methyl group, an ethyl group, a methoxy group, an ethoxy group are preferred, a methoxy group or an ethoxy group is more preferable.
　ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子およびヨウ素原子が挙げられる。 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
　Ｚ＋は、Ｎ＋（Ｒ１１）４、Ｎａ＋またはＫ＋であり、好ましくはＮ＋（Ｒ１１）４である。
　前記Ｎ＋（Ｒ１１）４としては、四つのＲ１１のうち、少なくとも二つが炭素数５～２０の１価の飽和炭化水素基であるものが好ましい。また、四つのＲ１１の合計炭素数は２０～８０であることが好ましく、２０～６０であることがより好ましい。化合物（１ａ）中にＮ＋（Ｒ１１）４が存在する場合、Ｒ１１がこれらの基であると、化合物（１ａ）を含む本発明の着色硬化性樹脂組成物から、異物が少ないカラーフィルタを形成できる。 Z + is N + (R 11 ) 4 , Na + or K + , preferably N + (R 11 ) 4 .
As the N + (R 11) 4, of the four R 11, at least those two is a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms are preferred. It is preferable that the total number of carbon atoms of the four R 11 is 20 to 80, and more preferably 20 to 60. When N + (R 11 ) 4 is present in the compound (1a), if R 11 is these groups, the color filter containing the compound (1a) and having less foreign matter can be obtained from the color curable resin composition of the present invention. Can be formed.
　化合物（１ａ）としては、式（２ａ）で表される化合物（以下「化合物（２ａ）」と記載することがある）が好ましい。化合物（２ａ）は、その互変異性体であってもよい。 As the compound (1a), a compound represented by the formula (2a) (hereinafter, may be referred to as “compound (2a)”) is preferable. Compound (2a) may be a tautomer thereof.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
［式（２ａ）中、Ｒ２１～Ｒ２４は、それぞれ独立に、水素原子、カルボキシ基を有していてもよい炭素数１～２０の１価の飽和炭化水素基、置換基を有していてもよい炭素数６～１０の１価の芳香族炭化水素基または＊－Ｒ１２－Ｓｉ（Ｒ１３）３で表される基（前記式中、＊は窒素原子との結合位置を表し）を表し、Ｒ２１およびＲ２２は、一緒になって窒素原子を含む環を形成してもよく、Ｒ２３およびＲ２４は、一緒になって窒素原子を含む環を形成してもよく、
　Ｒ２５は、－ＳＯ３ －、－ＳＯ３Ｈ、－ＳＯ３ －Ｚ１＋または－ＳＯ２ＮＨＲ２６を表し、
　ｍは、０～５の整数を表し、ｍが２以上のとき、複数のＲ２５は同一でも異なってもよく、
　ａは、０または１の整数を表し、
　Ｘは、ハロゲン原子を表し、
　Ｒ２６は、炭素数１～２０の１価の飽和炭化水素基を表し、
　Ｚ１＋は、Ｎ＋（Ｒ２７）４、Ｎａ＋またはＫ＋を表し、四つのＲ２７は同一でも異なってもよく、並びに
　Ｒ２７は、炭素数１～２０の１価の飽和炭化水素基またはベンジル基を表し、
　但し、式（２ａ）中にイオンの形態の－ＳＯ３ －が存在する場合、その数は１個である。］ [In the formula (2a), R 21 to R 24 each independently have a hydrogen atom and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent which may have a carboxy group. A monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a group represented by * -R 12- Si (R 13 ) 3 (in the above formula, * represents a bond position with a nitrogen atom). R 21 and R 22 may be combined to form a ring containing a nitrogen atom, and R 23 and R 24 may be combined to form a ring containing a nitrogen atom.
R 25 is, -SO 3 - represents Z1 + or -SO 2 NHR 26, -, -SO 3 H, -SO 3
m represents an integer from 0 to 5, and when m is 2 or more, a plurality of R 25s may be the same or different.
a represents an integer of 0 or 1 and represents
X represents a halogen atom
R 26 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
Z1 + represents N + (R 27 ) 4 , Na + or K + , the four R 27s may be the same or different, and R 27 is a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. Or represents a benzyl group
However, -SO 3 ions in the form in formula (2a) - if there is, the number is one. ]
　Ｒ２１～Ｒ２４における炭素数６～１０の１価の芳香族炭化水素基としては、例えば、前記Ｒ１～Ｒ４の芳香族炭化水素基として挙げたものと同様の基が挙げられる。前記芳香族炭化水素基が有していてもよい置換基としては、例えば、－ＳＯ３ －、－ＳＯ３Ｈ、－ＳＯ３ －Ｚ１＋、－ＳＯ３Ｒ２６または－ＳＯ２ＮＨＲ２６が挙げられる。
　Ｒ２１～Ｒ２４における＊－Ｒ１２－Ｓｉ（Ｒ１３）３で表される基の説明は、上記と同じである。 Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R 21 to R 24 include the same groups as those mentioned as the aromatic hydrocarbon group of R 1 to R 4 described above. The aromatic hydrocarbon group substituents which may be possessed by, for example, -SO 3 -, -SO 3 H , -SO 3 - Z1 +, -SO 3 R 26 or -SO 2 NHR 26 can be mentioned Be done.
The description of the group represented by * -R 12- Si (R 13 ) 3 in R 21 to R 24 is the same as above.
　Ｒ２１～Ｒ２４の組合せとしては、Ｒ２１およびＲ２３が水素原子であり、Ｒ２２およびＲ２４が炭素数６～１０の１価の芳香族炭化水素基であって、前記芳香族炭化水素基が、－ＳＯ３ －、－ＳＯ３Ｈ、－ＳＯ３ －Ｚ１＋、－ＳＯ３Ｒ２６または－ＳＯ２ＮＨＲ２６で置換されているものが好ましい。さらに好ましい組合せは、Ｒ２１およびＲ２３が水素原子であり、Ｒ２２およびＲ２４が炭素数６～１０の１価の芳香族炭化水素基であって、前記芳香族炭化水素基が、－ＳＯ３ －Ｚ１＋または－ＳＯ２ＮＨＲ２６で置換されていているものである。Ｒ２１～Ｒ２４がこれらの基であると、化合物（２ａ）を含む本発明の着色硬化性樹脂組成物から、耐熱性に優れるカラーフィルタを形成できる。 As a combination of R 21 to R 24 , R 21 and R 23 are hydrogen atoms, R 22 and R 24 are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the aromatic hydrocarbons are said to be. groups, -SO 3 -, -SO 3 H , -SO 3 - Z1 +, what is preferably substituted by -SO 3 R 26 or -SO 2 NHR 26. In a more preferable combination, R 21 and R 23 are hydrogen atoms, R 22 and R 24 are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the aromatic hydrocarbon group is -SO. 3 - Z1 + or those which have been substituted with -SO 2 NHR 26. When R 21 to R 24 are these groups, a color filter having excellent heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (2a).
　Ｒ２１およびＲ２２が一緒になって形成する窒素原子を含む環、並びに、Ｒ２３およびＲ２４が一緒になって形成する窒素原子を含む環としては、例えば、Ｒ１およびＲ２が一緒になって形成する環と同様のものが挙げられる。中でも、脂肪族複素環が好ましい。前記脂肪族複素環としては、例えば、下記のものが挙げられる。 Examples of the ring containing a nitrogen atom formed by R 21 and R 22 together and the ring containing a nitrogen atom formed by R 23 and R 24 together include R 1 and R 2 together. The same as the ring formed by Of these, an aliphatic heterocycle is preferable. Examples of the aliphatic heterocycle include the following.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　Ｒ２１～Ｒ２４、Ｒ２６およびＲ２７における炭素数１～２０の１価の飽和炭化水素基としては、例えば、Ｒ８～Ｒ１１において飽和炭化水素基として挙げたものと同様の基が挙げられる。
　Ｒ２１～Ｒ２４がカルボキシ基を有していてもよい炭素数１～２０の１価の飽和炭化水素基である場合、Ｒ２１～Ｒ２４は、それぞれ独立に、カルボキシ基を有していてもよいメチル基、カルボキシ基を有していてもよいエチル基、またはカルボキシ基を有していてもよいプロピル基であることが好ましい。また、－ＳＯ３Ｒ２６および－ＳＯ２ＮＨＲ２６におけるＲ２６としては、炭素数３～２０の分枝鎖状アルキル基が好ましく、炭素数６～１２の分枝鎖状アルキル基がより好ましく、２－エチルヘキシル基がさらに好ましい。Ｒ２６がこれらの基であると、化合物（２ａ）を含む本発明の着色硬化性樹脂組成物から、異物の発生が少ないカラーフィルタを形成できる。 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 21 to R 24 , R 26 and R 27 include the same groups as those mentioned as the saturated hydrocarbon group in R 8 to R 11 . Be done.
When R 21 to R 24 are monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms which may have a carboxy group, R 21 to R 24 each independently have a carboxy group. It is preferably a methyl group, an ethyl group which may have a carboxy group, or a propyl group which may have a carboxy group. As the R 26 in -SO 3 R 26 and -SO 2 NHR 26, preferably branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 6-12 carbon atoms, 2-Ethylhexyl groups are more preferred. When R 26 is these groups, a color filter containing less foreign matter can be formed from the colored curable resin composition of the present invention containing the compound (2a).
　Ｚ１＋は、Ｎ＋（Ｒ２７）４、Ｎａ＋またはＫ＋であり、好ましくはＮ＋（Ｒ２７）４である。前記Ｎ＋（Ｒ２７）４としては、四つのＲ２７のうち、少なくとも二つが炭素数５～２０の１価の飽和炭化水素基であることが好ましい。また、四つのＲ２７の合計炭素数は２０～８０が好ましく、２０～６０がより好ましい。化合物（２ａ）中にＮ＋（Ｒ２７）４が存在する場合、Ｒ２７がこれらの基であると、化合物（２ａ）を含む本発明の着色硬化性樹脂組成物から、異物の発生が少ないカラーフィルタを形成できる。
　ｍは、好ましく１～４であり、より好ましくは１または２である。 Z1 + is N + (R 27 ) 4 , Na + or K + , preferably N + (R 27 ) 4 . As the N + (R 27) 4, of the four R 27, it is preferred that at least two is a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. The total number of carbon atoms in the four R 27 is preferably 20 to 80, more preferably from 20 to 60. When N + (R 27 ) 4 is present in the compound (2a), when R 27 is these groups, the color curable resin composition of the present invention containing the compound (2a) produces less foreign matter. A color filter can be formed.
m is preferably 1 to 4, more preferably 1 or 2.
　また、化合物（１ａ）としては、式（３ａ）で表される化合物（以下「化合物（３ａ）」と記載することがある）も好ましい。化合物（３ａ）は、その互変異性体であってもよい。 Further, as the compound (1a), a compound represented by the formula (3a) (hereinafter, may be referred to as “compound (3a)”) is also preferable. Compound (3a) may be a tautomer thereof.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
［式（３ａ）中、Ｒ３１およびＲ３２は、それぞれ独立に、炭素数１～１０の１価の飽和炭化水素基、または＊－Ｒ１２－Ｓｉ（Ｒ１３）３で表される基（前記式中、＊は窒素原子との結合位置を表し）を表し、前記飽和炭化水素基は、炭素数６～１０の１価の芳香族炭化水素基、ハロゲン原子またはカルボキシ基で置換されていてもよく、前記飽和炭化水素基に含まれる－ＣＨ２－は、－Ｏ－、－ＣＯ－または－ＮＲ１１－で置き換わっていてもよく、前記芳香族炭化水素基は、炭素数１～３のアルコキシ基で置換されていてもよく、
　Ｒ３３およびＲ３４は、それぞれ独立に、炭素数１～４のアルキル基、炭素数１～４のアルキルスルファニル基または炭素数１～４のアルキルスルホニル基を表し、
　Ｒ３１およびＲ３３は、一緒になって窒素原子を含む環を形成してもよく、Ｒ３２およびＲ３４は、一緒になって窒素原子を含む環を形成してもよく、並びに
　ｐおよびｑは、それぞれ独立に、０～５の整数を表し、ｐが２以上のとき、複数のＲ３３は同一でも異なってもよく、ｑが２以上のとき、複数のＲ３４は同一でも異なってもよく、並びに
　Ｒ１１は、上記と同義である。］ [In formula (3a), R 31 and R 32 are independently monovalent saturated hydrocarbon groups having 1 to 10 carbon atoms, or groups represented by * -R 12- Si (R 13 ) 3 ( In the above formula, * represents the bond position with the nitrogen atom), and the saturated hydrocarbon group is substituted with a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, a halogen atom or a carboxy group. is -O - - -CH 2 is good, contained in the saturated hydrocarbon group, - CO- or -NR 11 - it may be replaced by the aromatic hydrocarbon groups, having 1 to 3 carbon atoms It may be substituted with an alkoxy group,
R 33 and R 34 independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.
R 31 and R 33 may be combined to form a ring containing a nitrogen atom, R 32 and R 34 may be combined to form a ring containing a nitrogen atom, and p and q. Each independently represents an integer of 0 to 5, and when p is 2 or more, a plurality of R 33s may be the same or different, and when q is 2 or more, a plurality of R 34s may be the same or different. Well, and R 11 are synonymous with the above. ]
　Ｒ３１およびＲ３２における炭素数１～１０の１価の飽和炭化水素は、直鎖状、分岐鎖状または環状のいずれでもよい。その例としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、イソプロピル基、イソブチル基、イソペンチル基、ネオペンチル基、２－エチルヘキシル基等の炭素数１～１０のアルキル基；シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基等の炭素数３～１０の脂環式飽和炭化水素基が挙げられる。
　Ｒ３１およびＲ３２における＊－Ｒ１２－Ｓｉ（Ｒ１３）３で表される基の説明は、上記と同じである。
　Ｒ３１およびＲ３２が置換基として有していてもよい炭素数６～１０の１価の芳香族炭化水素基としては、例えば、フェニル基が挙げられる。
　芳香族炭化水素基が置換基として有していてもよい炭素数１～３のアルキル基としては、例えば、メチル基、エチル基、プロピル基が挙げられる。
　芳香族炭化水素基が置換基として有していてもよい炭素数１～３のアルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基等が挙げられる。
　Ｒ３１およびＲ３２における＊－Ｒ１２－Ｓｉ（Ｒ１３）３で表される基の説明は、上記と同じである。
　Ｒ３１およびＲ３２は、それぞれ独立に、カルボキシ基を有していてもよい炭素数１～３の１価の飽和炭化水素基であることが好ましい。 The monovalent saturated hydrocarbons having 1 to 10 carbon atoms in R 31 and R 32 may be linear, branched or cyclic. Examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2 An alkyl group having 1 to 10 carbon atoms such as an ethylhexyl group; an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group can be mentioned.
The description of the group represented by * -R 12- Si (R 13 ) 3 in R 31 and R 32 is the same as above.
Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms that R 31 and R 32 may have as a substituent include a phenyl group.
Examples of the alkyl group having 1 to 3 carbon atoms that the aromatic hydrocarbon group may have as a substituent include a methyl group, an ethyl group and a propyl group.
Examples of the alkoxy group having 1 to 3 carbon atoms that the aromatic hydrocarbon group may have as a substituent include a methoxy group, an ethoxy group, a propoxy group and the like.
The description of the group represented by * -R 12- Si (R 13 ) 3 in R 31 and R 32 is the same as above.
It is preferable that R 31 and R 32 are monovalent saturated hydrocarbon groups having 1 to 3 carbon atoms, which may independently have a carboxy group.
　Ｒ３３およびＲ３４における炭素数１～４のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基等が挙げられる。
　Ｒ３３およびＲ３４における炭素数１～４のアルキルスルファニル基としては、例えば、メチルスルファニル基、エチルスルファニル基、プロピルスルファニル基、ブチルスルファニル基およびイソプロピルスルファニル基等が挙げられる。
　Ｒ３３およびＲ３４における炭素数１～４のアルキルスルホニル基としては、例えば、メチルスルホニル基、エチルスルホニル基、プロピルスルホニル基、ブチルスルホニル基およびイソプロピルスルホニル基等が挙げられる。
　Ｒ３３およびＲ３４は、好ましくは炭素数１～４のアルキル基であり、より好ましくはメチル基である。 Examples of the alkyl group having 1 to 4 carbon atoms in R 33 and R 34 include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and the like. ..
Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R 33 and R 34 include a methyl sulfanyl group, an ethyl sulfanyl group, a propyl sulfanyl group, a butyl sulfanyl group and an isopropyl sulfanyl group.
Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R 33 and R 34 include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group and an isopropylsulfonyl group.
R 33 and R 34 are preferably alkyl groups having 1 to 4 carbon atoms, and more preferably methyl groups.
　ｐおよびｑは、好ましくは０～２の整数であり、より好ましくは０または１である。 P and q are preferably integers of 0 to 2, and more preferably 0 or 1.
　化合物（１ａ）としては、例えば、式（１－１）～式（１－４５）で表される化合物が挙げられる。なお、下記式中のＲ４０は、炭素数１～２０の１価の飽和炭化水素基を表し、好ましくは炭素数６～１２の分枝鎖状アルキル基、より好ましくは２－エチルヘキシル基である。また、下記式中のＲ２６は、上記の通り、炭素数１～２０の１価の飽和炭化水素基を表す。 Examples of the compound (1a) include compounds represented by the formulas (1-1) to (1-45). R 40 in the following formula represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group. .. Further, R 26 in the following formula represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms as described above.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　キサンテン染料としては、Ｃ．Ｉ．アシッドレッド２８９のスルホンアミド化物、Ｃ．Ｉ．アシッドレッド２８９の４級アンモニウム塩、Ｃ．Ｉ．アシッドバイオレット１０２のスルホンアミド化物またはＣ．Ｉ．アシッドバイオレット１０２の第四級アンモニウム塩が好ましい。このような化合物としては、例えば、式（１－１）～式（１－８）、式（１－１１）または式（１－１２）で表される化合物が挙げられる。
　また、有機溶媒への溶解性に優れる点で、式（１－２４）～式（１－３３）、式（１－４４）および式（１－４５）のいずれかで表される化合物も好ましい。 Examples of the xanthene dye include C.I. I. Sulfonamides of Acid Red 289, C.I. I. Quaternary Ammonium Salt of Acid Red 289, C.I. I. Sulfonamides of Acid Violet 102 or C.I. I. A quaternary ammonium salt of Acid Violet 102 is preferred. Examples of such a compound include compounds represented by formulas (1-1) to (1-8), formulas (1-11) or formulas (1-12).
Further, a compound represented by any of the formulas (1-24) to (1-33), formula (1-44) and formula (1-45) is also preferable because of its excellent solubility in an organic solvent. ..
　キサンテン染料は、市販されているキサンテン染料（例えば、中外化成社製の「Chugai Aminol Fast Pink R-H/C」、田岡化学工業社製の「Rhodamin 6G」）を用いることができる。また、市販されているキサンテン染料を出発原料として、公知技術（例えば、特開２０１０－３２９９９号公報）を参考に合成することもできる。 As the xanthene dye, a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink R-H / C" manufactured by Chugai Pharmaceutical Co., Ltd. and "Rhodamin 6G" manufactured by Taoka Chemical Co., Ltd.) can be used. Further, it is also possible to synthesize using a commercially available xanthene dye as a starting material with reference to a known technique (for example, JP-A-2010-32999).
　トリアリールメタン染料は、好ましくは式（４ａ）： The triarylmethane dye is preferably of the formula (4a):
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
［式（４ａ）中、Ｒ１Ａ～Ｒ８Ａは、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、ヒドロキシ基、または炭素数１～２０の飽和炭化水素基を表し、前記飽和炭化水素基の炭素数が２～２０である場合、前記飽和炭化水素基に含まれる－ＣＨ２－は、－Ｏ－または－ＣＯ－で置き換わっていてもよく、
　Ｒ９Ａ～Ｒ１２Ａは、それぞれ独立に、水素原子、炭素数１～２０の飽和炭化水素基、置換基を有していてもよい炭素数６～２０の芳香族炭化水素基または置換基を有していてもよい炭素数７～３０のアラルキル基を表し、前記飽和炭化水素基は、置換若しくは非置換のアミノ基またはハロゲン原子で置換されていてもよく、前記飽和炭化水素基の炭素数が２～２０である場合、前記飽和炭化水素基に含まれる－ＣＨ２－は、－Ｏ－または－ＣＯ－で置き換わっていてもよく、Ｒ９ＡおよびＲ１０Ａが結合してそれらが結合する窒素原子とともに環を形成してもよく、Ｒ１１ＡおよびＲ１２Ａが結合してそれらが結合する窒素原子とともに環を形成してもよく、
　Ｒ１３Ａは、置換されていてもよい炭素数６～２０の芳香族炭化水素基を表し、
　［Ｇ］ｇ－は、任意のｇ価の対アニオンを表し、並びに
　ｇは、０または任意の自然数を表し、ｇが２以上の自然数である場合、式（４ａ）中の複数のカチオンは、それぞれ同一であっても異なっていてもよい。］
で表される化合物である。 [In the formula (4a), R 1A to R 8A independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or a saturated hydrocarbon group having 1 to 20 carbon atoms, and of the saturated hydrocarbon group. When the number of carbon atoms is 2 to 20, -CH 2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-.
Each of R 9A to R 12A independently has a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, and an aromatic hydrocarbon group or a substituent having 6 to 20 carbon atoms which may have a substituent. It represents an aralkyl group having 7 to 30 carbon atoms which may be used, and the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or a halogen atom, and the saturated hydrocarbon group has a carbon number of 7 to 30. When it is 2 to 20, -CH 2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-, and the nitrogen atom to which R 9A and R 10A are bonded to each other is bonded. They may form a ring with, or R 11A and R 12A may bond to form a ring with the nitrogen atom to which they bind.
R 13A represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted.
[G] g- represents a counter anion of arbitrary g valence, and g represents 0 or any natural number, and when g is a natural number of 2 or more, the plurality of cations in formula (4a) are They may be the same or different. ]
It is a compound represented by.
　クマリン染料は、分子内にクマリン骨格を有する化合物を含む染料である。クマリン染料としては、例えば、Ｃ．Ｉ．アシッドイエロー２２７、２５０；Ｃ．Ｉ．ディスパースイエロー８２、１８４；Ｃ．Ｉ．ソルベントオレンジ１１２；Ｃ．Ｉ．ソルベントイエロー１６０、１７２；特許第１２９９９４８号公報に記載のクマリン染料等が挙げられる。有機溶剤に溶解するものが好ましい。 A coumarin dye is a dye containing a compound having a coumarin skeleton in the molecule. Examples of the coumarin dye include C.I. I. Acid Yellow 227, 250; C.I. I. Disperse Yellow 82, 184; C.I. I. Solvent Orange 112; C.I. I. Solvent Yellow 160, 172; coumarin dyes and the like described in Japanese Patent No. 12999948. Those that dissolve in an organic solvent are preferable.
　上記のもの以外の染料としては、例えば、カラーインデックス（Ｔｈｅ　Ｓｏｃｉｅｔｙ　ｏｆ　Ｄｙｅｒｓ　ａｎｄ　Ｃｏｌｏｕｒｉｓｔｓ出版）に記載されている染料、染色ノート（色染社）に記載されている染料が挙げられる。また、染料としては、例えば、アゾ染料、シアニン染料、フタロシアニン染料、アントラキノン染料、ナフトキノン染料、キノンイミン染料、メチン染料、アゾメチン染料、スクアリリウム染料、アクリジン染料、スチリル染料、キノリン染料およびニトロ染料等が挙げられる。これらのうち、有機溶剤に溶解する染料が好ましい。 Examples of dyes other than the above include dyes listed in the Color Index (The Society of Dyers and Colorists Publishing) and dyes listed in the Dyeing Note (Color Dyeing Company). Examples of the dye include azo dye, cyanine dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acrydin dye, styryl dye, quinoline dye and nitro dye. .. Of these, dyes that dissolve in organic solvents are preferred.
　染料の具体例としては、以下のものが挙げられる。
（１）Ｃ．Ｉ．ソルベント染料
　Ｃ．Ｉ．ソルベントイエロー４、１４、１５、２３、２４、２５、３８、６２、６３、６８、７９、８１、８２、８３、８９、９４、９８、９９、１６２；
　Ｃ．Ｉ．ソルベントオレンジ２、７、１１、１５、２６、４１、５４、５６、９９；
　Ｃ．Ｉ．ソルベントレッド２４、４９、９０、９１、１１１、１１８、１１９、１２２、１２４、１２５、１２７、１３０、１３２、１４３、１４５、１４６、１５０、１５１、１５５、１６０、１６８、１６９、１７２、１７５、１８１、２０７、２２２、２２７、２３０、２４５、２４７；
　Ｃ．Ｉ．ソルベントバイオレット１１、１３、１４、２６、３１、３６、３７、３８、４５、４７、４８、５１、５９、６０；
　Ｃ．Ｉ．ソルベントブルー１４、１８、３５、３６、４５、５８、５９、５９：１、６３、６８、６９、７８、７９、８３、９４、９７、９８、１００、１０１、１０２、１０４、１０５、１１１、１１２、１２２、１２８、１３２、１３６、１３９；
　Ｃ．Ｉ．ソルベントグリーン１、３、５、２８、２９、３２、３３；等。 Specific examples of the dye include the following.
(1) C.I. I. Solvent dye C. I. Solvent Yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162;
C. I. Solvent Orange 2,7,11,15,26,41,54,56,99;
C. I. Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247;
C. I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;
C. I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
C. I. Solvent Green 1, 3, 5, 28, 29, 32, 33; etc.
（２）Ｃ．Ｉ．アシッド染料
　Ｃ．Ｉ．アシッドイエロー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．アシッドオレンジ６、７、８、１０、１２、２６、５０、５１、５２、５６、６２、６３、６４、７４、７５、９４、９５、１０７、１０８、１４９、１６２、１６９、１７３；
　Ｃ．Ｉ．アシッドレッド７３、８０、９１、９７、１３８、１５１、２１１，２７４；
　Ｃ．Ｉ．アシッドグリーン３、５、９、２５、２７、２８、４１；
　Ｃ．Ｉ．アシッドバイオレット３４、１２０；
　Ｃ．Ｉ．アシッドブルー２５、２７、４０、４５、７８、８０、１１２；等。 (2) C.I. I. Acid dye C. I. 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, 202, 203, 204, 205, 207, 212, 214, 220, 221 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;
C. I. Acid Red 73, 80, 91, 97, 138, 151, 211,274;
C. I. Acid Green 3, 5, 9, 25, 27, 28, 41;
C. I. Acid Violet 34, 120;
C. I. Acid Blue 25, 27, 40, 45, 78, 80, 112; etc.
（３）Ｃ．Ｉ．ベーシック染料
　Ｃ．Ｉ．ベーシックグリーン１；等。 (3) C.I. I. Basic dye C. I. Basic Green 1; etc.
（４）Ｃ．Ｉ．リアクティブ染料
　Ｃ．Ｉ．リアクティブイエロー２、７６、１１６；
　Ｃ．Ｉ．リアクティブオレンジ１６；等。 (4) C.I. I. Reactive dye C. I. Reactive Yellow 2,76,116;
C. I. Reactive orange 16; etc.
（５）Ｃ．Ｉ．ダイレクト染料
　Ｃ．Ｉ．ダイレクトイエロー２、４、２８、３３、３４、３５、３８、３９、４３、４４、４７、５０、５４、５８、６８、６９、７０、７１、８６、９３、９４、９５、９８、１０２、１０８、１０９、１２９、１３２、１３６、１３８、１４１；
　Ｃ．Ｉ．ダイレクトオレンジ２６、３４、３９、４１、４６、５０、５２、５６、５７、６１、６４、６５、６８、７０、９６、９７、１０６、１０７；
　Ｃ．Ｉ．ダイレクトブルー４０；等。 (5) C.I. I. Direct dye C. I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;
C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct blue 40; etc.
（６）Ｃ．Ｉ．ディスパース染料
　Ｃ．Ｉ．ディスパースイエロー５１、５４、７６；
　Ｃ．Ｉ．ディスパースバイオレット２６、２７；
　Ｃ．Ｉ．ディスパースブルー１、１４、５６、６０；等。 (6) C.I. I. Disperse dye C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse Violet 26, 27;
C. I. Disperse Blue 1, 14, 56, 60; etc.
（７）Ｃ．Ｉ．モーダント染料
　Ｃ．Ｉ．モーダントイエロー５、８、１０、１６、２０、２６、３０、３１、３３、４２、４３、４５、５６、６１、６２、６５；
　Ｃ．Ｉ．モーダントオレンジ３、４、５、８、１２、１３、１４、２０、２１、２３、２４、２８、２９、３２、３４、３５、３６、３７、４２、４３、４７、４８；等。 (7) C.I. I. Mordant dye C. I. Modant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; etc.
（８）Ｃ．Ｉ．バット染料
　Ｃ．Ｉ．バットグリーン１等。 (8) C.I. I. Vat dye C. I. Bat green 1st prize.
　顔料（Ａ２）としては、特に限定されず公知の顔料を使用することができ、例えば、カラーインデックス（Ｔｈｅ　Ｓｏｃｉｅｔｙ　ｏｆ　Ｄｙｅｒｓ　ａｎｄ　Ｃｏｌｏｕｒｉｓｔｓ出版）に記載の顔料が挙げられる。 As the pigment (A2), a known pigment can be used without particular limitation, and examples thereof include pigments described in the Color Index (The Society of Dyers and Colorists Publishing).
　顔料（Ａ２）としては、例えば、以下のものが挙げられる：
　Ｃ．Ｉ．ピグメントイエロー１、３、１２、１３、１４、１５、１６、１７、２０、２４、３１、５３、８３、８６、９３、９４、１０９、１１０、１１７、１２５、１２８、１２９、１３７、１３８、１３９、１４７、１４８、１５０、１５３、１５４、１６６、１７３、１９４、２１４などの黄色顔料；
　Ｃ．Ｉ．ピグメントオレンジ１３、３１、３６、３８、４０、４２、４３、５１、５５、５９、６１、６４、６５、７１、７３などのオレンジ色顔料；
　Ｃ．Ｉ．ピグメントレッド９、９７、１０５、１２２、１２３、１４４、１４９、１６６、１６８、１７６、１７７、１８０、１９２、２０９、２１５、２１６、２２４、２４２、２５４、２５５、２６４、２６５などの赤色顔料；
　Ｃ．Ｉ．ピグメントブルー１５、１５：３、１５：４、１５：６、６０などの青色顔料；
　Ｃ．Ｉ．ピグメントバイオレット１、１９、２３、２９、３２、３６、３８などのバイオレット色顔料；
　Ｃ．Ｉ．ピグメントグリーン７、３６、５８などの緑色顔料；
　Ｃ．Ｉ．ピグメントブラウン２３、２５などのブラウン色顔料；
　Ｃ．Ｉ．ピグメントブラック１、７などの黒色顔料等。 Examples of the pigment (A2) include the following:
C. I. Pigment Yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,129,137,138, Yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments;
C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments;
C. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other violet color pigments;
C. I. Pigment Green 7, 36, 58 and other green pigments;
C. I. Pigment brown 23, 25 and other brown pigments;
C. I. Black pigments such as Pigment Black 1 and 7.
　顔料（Ａ２）は、好ましくは赤色顔料または青色顔料である。
　赤色顔料は、５８０ｎｍ以下の波長域に吸収を有することが好ましく、４８０ｎｍ以上５６０ｎｍ以下の波長域に吸収を有することがより好ましい。また、前記赤色顔料は、６１０ｎｍ以上の波長域の光を透過するものであることが好ましい。 The pigment (A2) is preferably a red pigment or a blue pigment.
The red pigment preferably has absorption in a wavelength region of 580 nm or less, and more preferably has absorption in a wavelength region of 480 nm or more and 560 nm or less. Further, the red pigment preferably transmits light in a wavelength range of 610 nm or more.
　赤色顔料としては、公知の顔料を使用することができ、例えば、カラーインデックス（Ｔｈｅ　Ｓｏｃｉｅｔｙ　ｏｆ　Ｄｙｅｒｓ　ａｎｄ　Ｃｏｌｏｕｒｉｓｔｓ出版）に記載されているものが挙げられる。 As the red pigment, a known pigment can be used, and examples thereof include those described in the Color Index (The Society of Dyers and Colorists Publishing).
　赤色顔料の中でも、アントラキノン顔料、アゾ顔料、キナクリドン顔料、ペリレン顔料、ジケトピロロピロール顔料が好ましく、アントラキノン顔料およびジケトピロロピロール顔料がより好ましい。 Among the red pigments, anthraquinone pigments, azo pigments, quinacridone pigments, perylene pigments and diketopyrrolopyrrole pigments are preferable, and anthraquinone pigments and diketopyrrolopyrrole pigments are more preferable.
　好ましい赤色顔料の具体例としては、Ｃ．Ｉ．ピグメントレッド９、９７、１０５、１２２、１２３、１４４、１４９、１６６、１６８、１７６、１７７、１７９、１８０、１９２、２０２、２０８、２０９、２１５、２１６、２２４、２４２、２５４、２５５、２６４、２６５、２６６、２６８、２６９、２７３、および特開２０１３－０１４７５０に記載の式（Ｐ）で表される化合物等が挙げられる。これらの中で、Ｃ．Ｉ．ピグメントレッド１７７、２０８、２４２、２５４、２６９、および特開２０１３－０１４７５０に記載の式（Ｐ）で表される化合物がより好ましく、Ｃ．Ｉ．ピグメントレッド１７７、２５４、および特開２０１３－０１４７５０に記載の式（Ｐ）で表される化合物がさらに好ましい。 Specific examples of preferable red pigments include C.I. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 202, 208, 209, 215, 216, 224, 242, 254, 255, 264, Examples thereof include compounds represented by the formula (P) described in 265, 266, 268, 269, 273, and Japanese Patent Application Laid-Open No. 2013-014750. Among these, C.I. I. Pigment Red 177, 208, 242, 254, 269, and the compound represented by the formula (P) described in JP2013-014750 are more preferable, and C.I. I. Pigment Red 177, 254, and the compound represented by the formula (P) described in JP2013-014750 are more preferable.
　青色顔料は、７００ｎｍ以下の波長域に吸収を有することが好ましく、５８０ｎｍ以上６５０ｎｍ以下の波長域に吸収を有することがより好ましい。また、青色顔料は、４００ｎｍ以上の波長域の光を透過するものであることが好ましい。 The blue pigment preferably has absorption in the wavelength range of 700 nm or less, and more preferably has absorption in the wavelength range of 580 nm or more and 650 nm or less. Further, the blue pigment preferably transmits light in a wavelength range of 400 nm or more.
　青色顔料は、好ましくフタロシアニン顔料であり、より好ましくは銅フタロシアニン顔料および／または亜鉛フタロシアニン顔料であり、さらに好ましくはハロゲン化銅フタロシアニン顔料および／またはハロゲン化亜鉛フタロシアニン顔料であり、特に好ましくはハロゲン化銅フタロシアニン顔料である。 The blue pigment is preferably a phthalocyanine pigment, more preferably a copper phthalocyanine pigment and / or a zinc phthalocyanine pigment, still more preferably a copper halide phthalocyanine pigment and / or a halogenated zinc phthalocyanine pigment, and particularly preferably a copper halide. It is a phthalocyanine pigment.
　具体的には、Ｃ．Ｉ．ピグメントブルー１５、１５：３、１５：４、１５：６、６０が好ましく、Ｃ．Ｉ．ピグメントブルー１５、１５：３、１５：４、１５：６がより好ましく、Ｃ．Ｉ．ピグメントブルー１５：６が特に好ましい。前記の青色顔料を使用することによって、透過スペクトルの最適化が容易であり、カラーフィルタの耐光性および耐薬品性が良好になる。 Specifically, C.I. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 are preferred. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6 are more preferred, C.I. I. Pigment Blue 15: 6 is particularly preferred. By using the blue pigment, the transmission spectrum can be easily optimized, and the light resistance and chemical resistance of the color filter are improved.
　顔料は、必要に応じて、ロジン処理、酸性基または塩基性基が導入された顔料誘導体等を用いた表面処理、高分子化合物等による顔料表面へのグラフト処理、硫酸微粒化法等による微粒化処理、または不純物を除去するための有機溶剤や水等による洗浄処理、イオン性不純物のイオン交換法等による除去処理等が施されていてもよい。顔料は、粒径が均一であることが好ましい。 If necessary, the pigment is treated with a rosin, a surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, a graft treatment on the pigment surface with a polymer compound or the like, and atomization by a sulfuric acid atomization method or the like. Treatment, cleaning treatment with an organic solvent, water, etc. for removing impurities, removal treatment of ionic impurities by an ion exchange method, or the like may be performed. The pigment preferably has a uniform particle size.
　分散剤を使用して分散処理を行うことで、顔料が溶液中で均一に分散した状態の顔料分散液を得ることができる。 By performing the dispersion treatment using a dispersant, it is possible to obtain a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution.
　分散剤としては、例えば、界面活性剤が挙げられる。界面活性剤は、カチオン界面活性剤、アニオン界面活性剤、ノニオン界面活性剤、両性界面活性剤のいずれでもよい。界面活性剤としては、例えば、ポリエステル系界面活性剤、ポリアミン系界面活性剤、アクリル系界面活性剤等が挙げられる。分散剤の市販品としては、例えば、ＫＰ（信越化学工業社製）、フローレン（共栄社化学社製）、ソルスパース（登録商標）（ゼネカ社製）、ＥＦＫＡ（ＢＡＳＦ社製）、アジスパー（登録商標）（味の素ファインテクノ社製）、ＤＩＳＰＥＲＢＹＫ（登録商標）（ビックケミー社製）、ＢＹＫＬＰＮ（ＢＹＫ社製）などが挙げられる。 Examples of the dispersant include a surfactant. The surfactant may be any of a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant. Examples of the surfactant include polyester-based surfactants, polyamine-based surfactants, acrylic-based surfactants, and the like. Commercially available dispersants include, for example, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoei Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca), EFKA (manufactured by BASF), and Ajispar (registered trademark). (Ajinomoto Fine Techno Co., Ltd.), DISPERBYK (registered trademark) (Big Chemie Co., Ltd.), BYKLPN (manufactured by BYK Co., Ltd.) and the like.
　顔料分散液に分散剤が含まれる場合、その含有量は、顔料（Ａ２）１００重量部に対して、好ましくは１重量部以上５００重量部以下であり、より好ましくは５重量部以上３００重量部以下である。分散剤の含有量が前記の範囲内にあると、均一な分散状態の顔料分散液が得られる傾向がある。 When the pigment dispersion liquid contains a dispersant, the content thereof is preferably 1 part by weight or more and 500 parts by weight or less, and more preferably 5 parts by weight or more and 300 parts by weight with respect to 100 parts by weight of the pigment (A2). It is as follows. When the content of the dispersant is within the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.
　着色剤（Ａ）の含有量は、固形分の総量に対して、好ましくは１重量％以上、６０重量％以下であり、より好ましくは３重量％以上、５５重量％以下であり、さらに好ましくは５重量％以上、５０重量％以下である。本明細書における「固形分の総量」とは、着色硬化性樹脂組成物の総量から溶剤の含有量を除いた量のことをいう。着色剤（Ａ）の含有量が前記の範囲内にあると、色濃度が十分なカラーフィルタが得られる。また、着色剤（Ａ）の含有量が前記の範囲内にあると、組成物中に樹脂や重合性化合物を必要量含有させることができるので、機械的強度が十分なカラーフィルタを形成することができる。固形分の総量およびこれに対する各成分の含有量は、例えば、液体クロマトグラフィーまたはガスクロマトグラフィーなどの公知の分析手段で測定することができる。 The content of the colorant (A) is preferably 1% by weight or more and 60% by weight or less, more preferably 3% by weight or more and 55% by weight or less, still more preferably, with respect to the total amount of solid content. It is 5% by weight or more and 50% by weight or less. The "total amount of solid content" in the present specification means an amount obtained by subtracting the content of the solvent from the total amount of the colored curable resin composition. When the content of the colorant (A) is within the above range, a color filter having a sufficient color density can be obtained. Further, when the content of the colorant (A) is within the above range, a required amount of the resin or the polymerizable compound can be contained in the composition, so that a color filter having sufficient mechanical strength can be formed. Can be done. The total amount of solids and the content of each component relative to the total amount can be measured by a known analytical means such as liquid chromatography or gas chromatography.
　染料（Ａ１）を使用する場合、その含有量は、固形分の総量に対して、０．５重量％以上であることが好ましく、１重量％以上であることがより好ましく、６０重量％以下であることがより好ましく、５５重量％以下であることがさらに好ましい。染料（Ａ１）の含有量が前記範囲にあると、アルカリ現像液に対する現像性が良好な着色硬化性樹脂組成物を得ることができる。 When the dye (A1) is used, its content is preferably 0.5% by weight or more, more preferably 1% by weight or more, and 60% by weight or less, based on the total amount of solids. It is more preferable that the content is 55% by weight or less. When the content of the dye (A1) is within the above range, a colored curable resin composition having good developability with respect to an alkaline developer can be obtained.
　顔料（Ａ２）を使用する場合、その含有量は、固形分の総量に対して、１重量％以上であることが好ましく、１．５重量％以上であることがより好ましく、６０重量％以下であることが好ましく、５５重量％以下であることがより好ましく、５０重量％以下であることがさらに好ましい。顔料（Ａ２）の含有量が前記範囲にあると、色度が良好なカラーフィルタを得ることができる。 When the pigment (A2) is used, its content is preferably 1% by weight or more, more preferably 1.5% by weight or more, and 60% by weight or less, based on the total amount of solids. It is preferably 55% by weight or less, and further preferably 50% by weight or less. When the content of the pigment (A2) is within the above range, a color filter having a good chromaticity can be obtained.
　染料（Ａ１）および顔料（Ａ２）を使用する場合、染料（Ａ１）と顔料（Ａ２）との重量比（染料（Ａ１）：顔料（Ａ２））は、好ましくは１：９９～９９：１であり、より好ましくは１：９９～９５：５であり、特に好ましくは５：９５～９０：１０である。 When the dye (A1) and the pigment (A2) are used, the weight ratio of the dye (A1) to the pigment (A2) (dye (A1): pigment (A2)) is preferably 1:99 to 99: 1. Yes, more preferably 1:99 to 95: 5, and particularly preferably 5:95 to 90:10.
　本発明の一態様では、着色剤（Ａ）は、式（Ａ３－１）： In one aspect of the present invention, the colorant (A) is of formula (A3-1) :.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
で表される化合物（以下「化合物（Ａ３－１）」と記載することがある）、および式（Ａ３－２）： (Hereinafter referred to as "Compound (A3-1)"), and formula (A3-2):
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
で表される化合物（以下「化合物（Ａ３－２）」と記載することがある）からなる群から選ばれる少なくとも一つの化合物（Ａ３）を含む。 It contains at least one compound (A3) selected from the group consisting of the compound represented by (hereinafter, may be referred to as "compound (A3-2)").
　化合物（Ａ３）（即ち、化合物（Ａ３－１）および化合物（Ａ３－２））は、その構造（例えば、対イオンである（Ｍｒ＋）ｋ－１および［Ｙ］ｍ－の種類）によって、「溶剤に可溶な染料」または「溶剤に不溶な顔料」となる。即ち、化合物（Ａ３）の範囲には、染料である化合物および顔料である化合物の両方が含まれる。 Compound (A3) (ie, compound (A3-1) and compound (A3-2)) depends on its structure (eg, the type of counterion (Mr + ) k-1 and [Y] m- ). It becomes a "solvent-soluble dye" or a "solvent-insoluble pigment". That is, the range of the compound (A3) includes both the compound which is a dye and the compound which is a pigment.
　まず、化合物（Ａ３）中の基等の定義について説明する。特段の記載が無い限り、化合物（Ａ３）中の基等は、以下の定義を有する。
　ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。 First, the definition of groups and the like in compound (A3) will be described. Unless otherwise stated, the groups and the like in compound (A3) have the following definitions.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
　飽和炭化水素基は、直鎖状、分岐鎖状および環状のいずれでもよい。炭素数１～２０の飽和炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、ヘキサデシル基、イコシル基、イソプロピル基、イソブチル基、イソペンチル基、ネオペンチル基、２－エチルヘキシル基等の炭素数１～２０のアルキル基；シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、トリシクロデシル基等の炭素数３～２０の脂環式飽和炭化水素基が挙げられる。 The saturated hydrocarbon group may be linear, branched or cyclic. Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group and a hexadecyl group. , Icosyl group, isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group and other alkyl groups with 1 to 20 carbon atoms; cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, tri Examples thereof include an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclodecyl group.
　アルキル基は、直鎖状および分岐鎖状のいずれでもよい。炭素数１～１０のアルキル基の例としては、上述の炭素数１～２０のアルキル基の例示の中で炭素数が１～１０であるものが挙げられる。他の炭素数が異なるアルキル基の例示も同様である。また、アルキル基以外の基についても、炭素数が異なるものの例示は同様である。例えば、炭素数２～２０の飽和炭化水素基の例としては、上述の炭素数１～２０の飽和炭化水素基の例示の中で炭素数が２～２０であるものが挙げられる。 The alkyl group may be either linear or branched. Examples of the alkyl group having 1 to 10 carbon atoms include those having 1 to 10 carbon atoms in the above-mentioned examples of the alkyl group having 1 to 20 carbon atoms. The same applies to the examples of other alkyl groups having different carbon atoms. The same applies to groups other than alkyl groups, although they have different carbon atoms. For example, examples of saturated hydrocarbon groups having 2 to 20 carbon atoms include those having 2 to 20 carbon atoms in the above-mentioned examples of saturated hydrocarbon groups having 1 to 20 carbon atoms.
　アルカンジイル基は、直鎖状および分岐鎖状のいずれでもよい。炭素数１～１０のアルカンジイル基としては、例えば、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、イソプロピレン基、イソブチレン基、２－メチルトリメチレン基、イソペンチレン基、イソヘキシレン基、イソオクチレン基、２－エチルへキシレン基等が挙げられる。 The alkanediyl group may be either linear or branched. Examples of the arcandyl group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an isopropylene group, an isobutylene group, a 2-methyltrimethylene group and an isopentylene. Examples thereof include a group, an isohexylene group, an isooctylene group and a 2-ethylhexylene group.
　フルオロアルキル基は、直鎖状および分岐鎖状のいずれでもよい。炭素数１～１２のフルオロアルキル基としては、例えば、モノフルオロメチル基、ジフルオロメチル基、ペルフルオロメチル基、モノフルオロエチル基、ジフルオロエチル基、トリフルオロエチル基、テトラフルオロエチル基、ペルフルオロエチル基、モノフルオロプロピル基、ジフルオロプロピル基、トリフルオロプロピル基、テトラフルオロプロピル基、ペンタフルオロプロピル基、ヘキサフルオロプロピル基、ペルフルオロプロピル基、モノフルオロブチル基、ジフルオロブチル基、トリフルオロブチル基、テトラフルオロブチル基、ペンタフルオロブチル基、ヘキサフルオロブチル基、ヘプタフルオロブチル基、オクタフルオロブチル基、ペルフルオロブチル基が挙げられる。 The fluoroalkyl group may be either linear or branched. Examples of the fluoroalkyl group having 1 to 12 carbon atoms include a monofluoromethyl group, a difluoromethyl group, a perfluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, and a perfluoroethyl group. Monofluoropropyl group, difluoropropyl group, trifluoropropyl group, tetrafluoropropyl group, pentafluoropropyl group, hexafluoropropyl group, perfluoropropyl group, monofluorobutyl group, difluorobutyl group, trifluorobutyl group, tetrafluorobutyl Examples thereof include a group, a pentafluorobutyl group, a hexafluorobutyl group, a heptafluorobutyl group, an octafluorobutyl group and a perfluorobutyl group.
　アルコキシ基は、直鎖状および分岐鎖状のいずれでもよい。炭素数１～６のアルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、イソプロポキシ基、イソブトキシ基、イソペンチルオキシ基、ネオペンチルオキシ基が挙げられる。 The alkoxy group may be either linear or branched. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an isopropoxy group, an isobutoxy group, an isopentyloxy group and a neopentyloxy group. Can be mentioned.
　炭素数６～１４の芳香族炭化水素基としては、例えば、例えば、フェニル基、１－ナフチル基、２－ナフチル基、１－アントリル基、２－アントリル基、９－アントリル基が挙げられる。 Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, and a 9-anthryl group.
　炭素数７～３０のアラルキル基としては、例えば、ベンジル基、フェネチル基、ナフチルメチル基、３－フェニルプロピル基が挙げられる。 Examples of the aralkyl group having 7 to 30 carbon atoms include a benzyl group, a phenethyl group, a naphthylmethyl group, and a 3-phenylpropyl group.
　含窒素複素環は、単環および縮合環のいずれでもよい。３～１０員の含窒素複素環としては、例えば、ピロリジン環、モルホリン環、ピペリジン環、ピペラジン環が挙げられる。 The nitrogen-containing heterocycle may be either a monocyclic ring or a condensed ring. Examples of the 3- to 10-membered nitrogen-containing heterocycle include a pyrrolidine ring, a morpholine ring, a piperidine ring, and a piperazine ring.
　芳香族炭化水素環は、単環および縮合環のいずれでもよい。炭素数６～１４の芳香族炭化水素環は、ベンゼン環、ナフタレン環、フェナントレン環およびアントラセン環のいずれでもよい。 The aromatic hydrocarbon ring may be either a monocyclic ring or a condensed ring. The aromatic hydrocarbon ring having 6 to 14 carbon atoms may be any of a benzene ring, a naphthalene ring, a phenanthrene ring and an anthracene ring.
　芳香族複素環は、単環および縮合環のいずれでもよい。５～１０員の芳香族複素環としては、例えば、ピロール環、オキサゾール環、ピラゾール環、イミダゾール環、チアゾール環、フラン環、チオフェン環、ピリジン環、ピリミジン環、ピリダジン環、ピラジン環、インドール環、ベンズイミダゾール環、ベンゾチアゾール環、キノリン環、ベンゾフラン環等が挙げられる。 The aromatic heterocycle may be either a monocyclic ring or a condensed ring. Examples of the 5- to 10-membered aromatic heterocycle include a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, a thiazole ring, a furan ring, a thiophene ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, and an indole ring. Examples thereof include a benzimidazole ring, a benzothiazole ring, a quinoline ring, and a benzofuran ring.
　次に、式（Ａ３－１）中の基等について説明する。
　式（Ａ３－１）中のＲ４１ａおよびＲ４２ａは、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１～２０の飽和炭化水素基、置換基を有していてもよい炭素数６～１４の芳香族炭化水素基、または置換基を有していてもよい炭素数７～３０のアラルキル基を表すか、或いはＲ４１ａとＲ４２ａとが結合して、それらが結合する窒素原子と共に３～１０員の含窒素複素環を形成する。 Next, the groups and the like in the formula (A3-1) will be described.
R 41a and R 42a in the formula (A3-1) each independently have a hydrogen atom and a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and a substituent. It represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R 41a and R 42a are bonded to each other. It forms a 3- to 10-membered nitrogen-containing heterocycle with the bonding nitrogen atom.
　式（Ａ３－１）中の炭素数１～２０の飽和炭化水素基が有していてもよい置換基は、ハロゲン原子、ヒドロキシ基、ホルミル基およびアミノ基からなる群から選ばれる少なくとも一つである。 The substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (A3-1) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group. is there.
　式（Ａ３－１）中の炭素数１～２０の飽和炭化水素基が炭素数２～２０の飽和炭化水素基である場合、前記飽和炭化水素基に含まれる－ＣＨ２－は、－Ｏ－または－ＣＯ－に置き換わっていてもよい。ここで前記－ＣＨ２－には、窒素原子と結合している－ＣＨ２－および前記飽和炭化水素基の末端であるメチル基中の－ＣＨ２－は含まれない。また、前記飽和炭化水素基に含まれる－ＣＨ２－ＣＨ２－が、－Ｏ－Ｏ－または－ＣＯ－ＣＯ－に置き換わることはない。 When the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (A3-1) is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH 2- contained in the saturated hydrocarbon group is -O-. Alternatively, it may be replaced with -CO-. Here, -CH 2- does not include -CH 2 -bonded to a nitrogen atom and -CH 2- in the methyl group at the end of the saturated hydrocarbon group. Further, -CH 2- CH 2- contained in the saturated hydrocarbon group is not replaced with -O-O- or -CO-CO-.
　式（Ａ３－１）中の炭素数６～１４の芳香族炭化水素基が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、－ＳＯ３ －、－ＳＯ２－Ｎ－－ＳＯ２－Ｒｆ、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つである。 Aromatic hydrocarbon group substituents which may be possessed by the carbon number of 6 to 14 in the formula (A3-1) is a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - it is at least one selected from the group consisting of an alkyl group of -SO 2 -R f, and substituents to 1 carbon atoms which may have a 8.
　式（Ａ３－１）中の炭素数７～３０のアラルキル基が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、－ＳＯ３ －、－ＳＯ２－Ｎ－－ＳＯ２－Ｒｆ、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つである。
　式（Ａ３－１）中のＲｆは、炭素数１～１２のフルオロアルキル基を表す。 Substituents which may have an aralkyl group having 7 to 30 carbon atoms in the formula (A3-1) is a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - -SO 2- R f , and at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have substituents.
R f in the formula (A3-1) represents a fluoroalkyl group having 1 to 12 carbon atoms.
　式（Ａ３－１）中の炭素数１～８のアルキル基が有していてもよい置換基は、ハロゲン原子、ヒドロキシ基、ホルミル基およびアミノ基からなる群から選ばれる少なくとも一つである。 The substituent that the alkyl group having 1 to 8 carbon atoms in the formula (A3-1) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
　式（Ａ３－１）中の炭素数１～８のアルキル基が炭素数２～８のアルキル基である場合、前記アルキル基に含まれる－ＣＨ２－は、－Ｏ－または－ＣＯ－に置き換わっていてもよい。ここで前記－ＣＨ２－には、前記アルキル基の末端であるメチル基中の－ＣＨ２－は含まれない。また、前記アルキル基に含まれる－ＣＨ２－ＣＨ２－が、－Ｏ－Ｏ－または－ＣＯ－ＣＯ－に置き換わることはない。 When the alkyl group having 1 to 8 carbon atoms in the formula (A3-1) is an alkyl group having 2 to 8 carbon atoms, -CH 2- contained in the alkyl group is replaced with -O- or -CO-. May be. Wherein the -CH 2 - The, -CH 2 in a methyl group is the terminal of the alkyl group - is not included. Further, -CH 2- CH 2- contained in the alkyl group is not replaced with -OO- or -CO-CO-.
　Ｒ４１ａは、好ましくは水素原子または炭素数１～８のアルキル基、より好ましくは水素原子または炭素数１～４のアルキル基、さらに好ましくは炭素数１～４のアルキル基である。
　Ｒ４２ａは、好ましくは炭素数１～８のアルキル基および－ＳＯ３ －からなる群から選ばれる少なくとも一つの置換基を有していてもよいフェニル基、より好ましくは置換基として１個または２個の炭素数１～８のアルキル基を有し、且つ－ＳＯ３ －を有していてもよいフェニル基、さらに好ましくは置換基として１個または２個の炭素数１～４のアルキル基を有し、且つ－ＳＯ３ －を有していてもよいフェニル基である。 R 41a is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms.
R 42a is preferably an alkyl group and -SO 3 having 1 to 8 carbon atoms - one as at least one substituent a phenyl group which may have a, more preferably substituent selected from the group consisting or 2 It has a number of alkyl group having 1 to 8 carbon atoms, and -SO 3 - a phenyl group optionally having a, more preferably one or two alkyl groups having 1 to 4 carbon atoms as a substituent a, and -SO 3 - is a phenyl group which may have a.
　式（Ａ３－１）中のＲ４３ａおよびＲ４４ａは、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１～２０の飽和炭化水素基、置換基を有していてもよい炭素数６～１４の芳香族炭化水素基、または置換基を有していてもよい炭素数７～３０のアラルキル基を表すか、或いはＲ４３ａとＲ４４ａとが結合してそれらが結合する窒素原子と共に３～１０員の含窒素複素環を形成する。 R 43a and R 44a in the formula (A3-1) each independently have a hydrogen atom and a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and a substituent. It represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R 43a and R 44a are bonded to each other. It forms a 3- to 10-membered nitrogen-containing heterocycle with the nitrogen atom.
　Ｒ４３ａは、好ましくは水素原子または炭素数１～８のアルキル基、より好ましくは水素原子または炭素数１～４のアルキル基、さらに好ましくは炭素数１～４のアルキル基である。
　Ｒ４４ａは、好ましくは炭素数１～８のアルキル基および－ＳＯ３ －からなる群から選ばれる少なくとも一つの置換基を有していてもよいフェニル基、より好ましくは置換基として１個または２個の炭素数１～８のアルキル基を有し、且つ－ＳＯ３ －を有していてもよいフェニル基、さらに好ましくは置換基として１個または２個の炭素数１～４のアルキル基を有し、且つ－ＳＯ３ －を有していてもよいフェニル基である。 R 43a is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms.
R 44a is preferably an alkyl group and -SO 3 having 1 to 8 carbon atoms - one as at least one substituent a phenyl group which may have a, more preferably substituent selected from the group consisting or 2 It has a number of alkyl group having 1 to 8 carbon atoms, and -SO 3 - a phenyl group optionally having a, more preferably one or two alkyl groups having 1 to 4 carbon atoms as a substituent a, and -SO 3 - is a phenyl group which may have a.
　式（Ａ３－１）中のＲ４７ａ～Ｒ５４ａは、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、ヒドロキシ基、－ＳＯ３ －、－ＳＯ２－Ｎ－－ＳＯ２－Ｒｆ、または置換基を有していてもよい炭素数１～８のアルキル基を表す。Ｒ４７ａ～Ｒ５４ａは、それぞれ独立して、好ましくは水素原子、炭素数１～８のアルキル基または－ＳＯ３ －であり、より好ましくは水素原子または－ＳＯ３ －である。 R 47a ~ R 54a in formula (A3-1) are each independently a hydrogen atom, a halogen atom, a nitro group, hydroxy group, -SO 3 -, -SO 2 -N - -SO 2 -R f, Alternatively, it represents an alkyl group having 1 to 8 carbon atoms which may have a substituent. R 47a ~ R 54a are each independently preferably a hydrogen atom, an alkyl group or -SO 3 having 1 to 8 carbon atoms - a -, more preferably a hydrogen atom or -SO 3.
　式（Ａ３－１）中の環Ｔ１ａは、置換基を有していてもよい炭素数６～１４の芳香族炭化水素環または置換基を有していてもよい５～１０員の芳香族複素環を表す。 The ring T 1a in the formula (A3-1) may have a substituent and may have an aromatic hydrocarbon ring having 6 to 14 carbon atoms or a 5 to 10-membered aromatic which may have a substituent. Represents a heterocycle.
　式（Ａ３－１）中の炭素数６～１４の芳香族炭化水素環が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、－ＳＯ３ －、－ＳＯ２－Ｎ－－ＳＯ２－Ｒｆ、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つである。 Aromatic hydrocarbon ring substituent which may be possessed by the carbon number of 6 to 14 in the formula (A3-1) is a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - it is at least one selected from the group consisting of an alkyl group of -SO 2 -R f, and substituents to 1 carbon atoms which may have a 8.
　式（Ａ３－１）中の５～１０員の芳香族複素環が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、－ＳＯ３ －、－ＳＯ２－Ｎ－－ＳＯ２－Ｒｆ、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つである。 5-10 membered aromatic heterocyclic ring substituent which may have a in the formula (A3-1) is a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N It is at least one selected from the group consisting of --SO 2- R f , and an alkyl group having 1 to 8 carbon atoms which may have a substituent.
　環Ｔ１ａは、好ましくは式（１ｔ）： Ring T 1a is preferably of formula (1t):
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
で表される環である。
　式（１ｔ）中のＲ４５ａおよびＲ４６ａは、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１～２０の飽和炭化水素基、置換基を有していてもよい炭素数６～１４の芳香族炭化水素基、または置換基を有していてもよい炭素数７～３０のアラルキル基を表すか、或いはＲ４５ａとＲ４６ａとが結合して、それらが結合する窒素原子と共に３～１０員の含窒素複素環を形成する。 It is a ring represented by.
R 45a and R 46a in the formula (1t) may independently have a hydrogen atom and a substituent, and may have a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent. It represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R 45a and R 46a are bonded to each other. It forms a 3- to 10-membered nitrogen-containing heterocycle with a nitrogen atom.
　式（１ｔ）中の炭素数１～２０の飽和炭化水素基が有していてもよい置換基は、ハロゲン原子、ヒドロキシ基、ホルミル基およびアミノ基からなる群から選ばれる少なくとも一つである。 The substituent that the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (1t) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
　式（１ｔ）中の炭素数６～１４の芳香族炭化水素基が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、－ＳＯ３ －、－ＳＯ２－Ｎ－－ＳＯ２－Ｒｆ、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つである。 Aromatic hydrocarbon group substituents which may be possessed by the carbon number of 6 to 14 in the formula (1t) is a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N It is at least one selected from the group consisting of --SO 2- R f , and an alkyl group having 1 to 8 carbon atoms which may have a substituent.
　式（１ｔ）中の炭素数７～３０のアラルキル基が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、－ＳＯ３ －、－ＳＯ２－Ｎ－－ＳＯ２－Ｒｆ、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つである。 Substituents which may have an aralkyl group having 7 to 30 carbon atoms in the formula (1t) is a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - -SO It is at least one selected from the group consisting of 2- R f , and an alkyl group having 1 to 8 carbon atoms which may have a substituent.
　式（１ｔ）中の炭素数１～８のアルキル基が有していてもよい置換基は、ハロゲン原子、ヒドロキシ基、ホルミル基およびアミノ基からなる群から選ばれる少なくとも一つである。 The substituent that the alkyl group having 1 to 8 carbon atoms in the formula (1t) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
　Ｒ４５ａは、好ましくは水素原子または炭素数１～８のアルキル基、より好ましくは水素原子または炭素数１～４のアルキル基、さらに好ましくは炭素数１～４のアルキル基である。 R 45a is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms.
　Ｒ４６ａは、好ましくは炭素数１～８のアルキル基および－ＳＯ３ －からなる群から選ばれる少なくとも一つの置換基を有していてもよいフェニル基、より好ましくは置換基として１個または２個の炭素数１～８のアルキル基を有し、且つ－ＳＯ３ －を有していてもよいフェニル基、さらに好ましくは置換基として１個または２個の炭素数１～４のアルキル基を有し、且つ－ＳＯ３ －を有していてもよいフェニル基である。 R 46a is preferably an alkyl group and -SO 3 having 1 to 8 carbon atoms - one as at least one substituent a phenyl group which may have a, more preferably substituent selected from the group consisting or 2 It has a number of alkyl group having 1 to 8 carbon atoms, and -SO 3 - a phenyl group optionally having a, more preferably one or two alkyl groups having 1 to 4 carbon atoms as a substituent a, and -SO 3 - is a phenyl group which may have a.
　式（１ｔ）中のＲ５６ａは、水素原子、置換基を有していてもよい炭素数１～２０の飽和炭化水素基、置換基を有していてもよい炭素数６～１４の芳香族炭化水素基、または置換基を有していてもよい炭素数７～３０のアラルキル基を表す。 R 56a in the formula (1t) is a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and an aromatic having 6 to 14 carbon atoms which may have a substituent. Represents an aralkyl group having 7 to 30 carbon atoms which may have a hydrocarbon group or a substituent.
　Ｒ５６ａは、好ましくはハロゲン原子、炭素数１～８のアルキル基および－ＳＯ３ －からなる群から選ばれる少なくとも一つの置換基を有していてもよいフェニル基、より好ましくは置換基として１個または２個のハロゲン原子を有し、且つ－ＳＯ３ －を有していてもよいフェニル基、さらに好ましくは置換基として１個または２個のフッ素原子を有し、且つ－ＳＯ３ －を有していてもよいフェニル基である。 R 56a is preferably a halogen atom, an alkyl group and -SO 3 having 1 to 8 carbon atoms - 1 least one substituent a phenyl group which may have a selected from the group consisting of, more preferably a substituent It has a number or two halogen atoms, and -SO 3 - a phenyl group which may have a, more preferably has one or two fluorine atom as a substituent, and -SO 3 - and It is a phenyl group that may have.
　式（１ｔ）中のＬ１ａは、硫黄原子、酸素原子または－ＮＲ５７ａ－を表す。Ｒ５７ａは、水素原子または炭素数１～１０のアルキル基を表す。Ｌ１ａは、好ましくは硫黄原子である。 L 1a in the formula (1t) represents a sulfur atom, an oxygen atom or -NR 57a- . R 57a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. L 1a is preferably a sulfur atom.
　式（１ｔ）中の＊は、カルボカチオンとの結合位置を表す。言い換えると、式（１ｔ）中の－＊は、結合を表す。他の式中の－＊も、同様に結合を表す。 * In the formula (1t) represents the bond position with the carbocation. In other words, − * in equation (1t) represents a bond. -* In other equations also represents a bond.
　式（Ａ３－１）中のｒは、１以上の整数を表す。ｒは、好ましくは２である。ｒが２以上の整数である場合、式（Ａ３－１ａ）： R in the formula (A3-1) represents an integer of 1 or more. r is preferably 2. When r is an integer of 2 or more, the equation (A3-1a):
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
［式（Ａ３－１ａ）中、環Ｔ１ａ、Ｒ４１ａ～Ｒ４４ａおよびＲ４７ａ～Ｒ５４ａは、それぞれ、上記と同義である。］
で表される複数のアニオンは、同一でも、異なっていてもよい。式（Ａ３－１ａ）で表されるアニオンを、以下「アニオン（Ａ３ー１ａ）」と記載することがある。複数のアニオン（Ａ３－１ａ）は、同一であることが好ましい。 [In the formula (A3-1a), the rings T 1a , R 41a to R 44a and R 47a to R 54a are synonymous with the above, respectively. ]
The plurality of anions represented by may be the same or different. The anion represented by the formula (A3-1a) may be hereinafter referred to as "anion (A3-1a)". The plurality of anions (A3-1a) are preferably the same.
　式（Ａ３－１）中のｋは、アニオン（Ａ３－１ａ）が有する－ＳＯ３ －および－ＳＯ２－Ｎ－－ＳＯ２－Ｒｆの個数の合計を表し、且つ２以上の整数である。ｋは、好ましくは２である。 K in the formula (A3-1) are, -SO 3 anion (A3-1a) has - and -SO 2 -N - represents the total number of -SO 2 -R f, and is an integer of 2 or more .. k is preferably 2.
　式（Ａ３－１）中のＭｒ＋は、水素イオン、ｒ価の金属イオンまたはＮ＋（Ｒ５５ａ）４を表し、四つのＲ５５ａは同一でも、異なっていてもよい。Ｒ５５ａは、水素原子、炭素数１～２０の飽和炭化水素基または炭素数７～１０のアラルキル基を表す。式（Ａ３－１）中のｋ－１が２以上の整数である場合、複数のＭｒ＋は、同一でも、異なっていてもよい。 Mr + in the formula (A3-1) represents a hydrogen ion, an r-valent metal ion or N + (R 55a ) 4 , and the four R 55a may be the same or different. R 55a represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. When k-1 in the formula (A3-1) is an integer of 2 or more, the plurality of Mr + may be the same or different.
　Ｍｒ＋は、好ましくはｒ価の金属イオンである。ｒ価の金属イオンとしては、例えば、リチウムイオン、ナトリウムイオン、カリウムイオン等のアルカリ金属イオン；ベリリウムイオン、マグネシウムイオン、カルシウムイオン、ストロンチウムイオン、バリウムイオン等のアルカリ土類金属イオン；チタンイオン、ジルコニウムイオン、クロムイオン、マンガンイオン、鉄イオン、コバルトイオン、ニッケルイオン、銅イオン等の遷移金属イオン；亜鉛イオン、カドミウムイオン、アルミニウムイオン、インジウムイオン、錫イオン、鉛イオン、ビスマスイオン等の典型金属イオンが挙げられる。 Mr + is preferably an r-valent metal ion. Examples of the r-valent metal ion include alkali metal ions such as lithium ion, sodium ion and potassium ion; alkaline earth metal ions such as beryllium ion, magnesium ion, calcium ion, strontium ion and barium ion; titanium ion and zirconium. Transition metal ions such as ions, chromium ions, manganese ions, iron ions, cobalt ions, nickel ions and copper ions; typical metal ions such as zinc ions, cadmium ions, aluminum ions, indium ions, tin ions, lead ions and bismuth ions. Can be mentioned.
　Ｍｒ＋は、より好ましくは２価の金属イオンであり、さらに好ましくはアルカリ土類金属イオンであり、特に好ましくはバリウムイオン（Ｂａ２＋）である。 Mr + is more preferably a divalent metal ion, more preferably an alkaline earth metal ion, and particularly preferably a barium ion (Ba 2+ ).
　化合物（Ａ３－１）としては、
　Ｒ４１ａおよびＲ４３ａが、それぞれ独立して、水素原子または炭素数１～８のアルキル基であり、
　Ｒ４２ａおよびＲ４４ａが、それぞれ独立して、炭素数１～８のアルキル基および－ＳＯ３ －からなる群から選ばれる少なくとも一つの置換基を有していてもよいフェニル基であり、
　Ｒ４７ａ～Ｒ５４ａが、それぞれ独立して、水素原子、炭素数１～８のアルキル基または－ＳＯ３ －であり
　環Ｔ１ａが、上記式（１ｔ）で表される環であり［式（１ｔ）中、Ｒ４５ａが、水素原子または炭素数１～８のアルキル基であり、
　Ｒ４６ａが、炭素数１～８のアルキル基および－ＳＯ３ －からなる群から選ばれる少なくとも一つの置換基を有していてもよいフェニル基であり、
　Ｒ５６ａが、ハロゲン原子、炭素数１～８のアルキル基および－ＳＯ３ －からなる群から選ばれる少なくとも一つの置換基を有していてもよいフェニル基であり、
　Ｌ１ａが、硫黄原子であり、並びに
　＊は、カルボカチオンとの結合位置を表す。］、
　ｒが、２であり、
　ｋが、アニオン（Ａ３－１ａ）が有する－ＳＯ３ －の個数の合計を表し、且つ２であり、
　二つのアニオン（Ａ３－１ａ）が、同一であり、並びに
　Ｍｒ＋が、Ｂａ２＋である
化合物（以下「化合物（Ａ３－１’）」と記載することがある）が好ましい。 As the compound (A3-1),
R 41a and R 43a are independently hydrogen atoms or alkyl groups having 1 to 8 carbon atoms.
R 42a and R 44a are each independently an alkyl group and -SO 3 having 1 to 8 carbon atoms - at least one of which may have a substituent phenyl group selected from the group consisting of,
R 47a ~ R 54a are each independently a hydrogen atom, an alkyl group or -SO 3 having 1 to 8 carbon atoms - and ring T 1a is a ring represented by the above formula (1t) [wherein ( In 1t), R 45a is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R 46a is an alkyl group and -SO 3 having 1 to 8 carbon atoms - at least one of which may have a substituent phenyl group selected from the group consisting of,
R 56a is a halogen atom, an alkyl group and -SO 3 having 1 to 8 carbon atoms - at least one of which may have a substituent phenyl group selected from the group consisting of,
L 1a is a sulfur atom, and * represents a bond position with a carbocation. ],
r is 2,
k is, -SO 3 anions (A3-1a) has - represents the total number of a and 2,
A compound in which the two anions (A3-1a) are the same and Mr + is Ba 2+ (hereinafter, may be referred to as “compound (A3-1')”) is preferable.
　化合物（Ａ３－１’）において、Ｒ４１ａおよびＲ４３ａは、より好ましくは水素原子または炭素数１～４のアルキル基、さらに好ましくは炭素数１～４のアルキル基であり、Ｒ４２ａおよびＲ４４ａは、それぞれ独立して、より好ましくは置換基として１個または２個の炭素数１～８のアルキル基を有し、且つ－ＳＯ３ －を有していてもよいフェニル基、さらに好ましくは置換基として１個または２個の炭素数１～４のアルキル基を有し、且つ－ＳＯ３ －を有していてもよいフェニル基であり、Ｒ４７ａ～Ｒ５４ａは、より好ましくは水素原子または－ＳＯ３ －であり、Ｒ４５ａは、より好ましくは水素原子または炭素数１～４のアルキル基、さらに好ましくは炭素数１～４のアルキル基であり、Ｒ４６ａは、より好ましくは置換基として１個または２個の炭素数１～８のアルキル基を有し、且つ－ＳＯ３ －を有していてもよいフェニル基、さらに好ましくは置換基として１個または２個の炭素数１～４のアルキル基を有し、且つ－ＳＯ３ －を有していてもよいフェニル基であり、並びにＲ５６ａは、より好ましくは置換基として１個または２個のハロゲン原子を有し、且つ－ＳＯ３ －を有していてもよいフェニル基、さらに好ましくは置換基として１個または２個のフッ素原子を有し、且つ－ＳＯ３ －を有していてもよいフェニル基である。 In the compound (A3-1'), R 41a and R 43a are more preferably hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, still more preferably alkyl groups having 1 to 4 carbon atoms, and R 42a and R 44a. are each independently more preferably has one or two alkyl groups having 1 to 8 carbon atoms as a substituent, and -SO 3 - a phenyl group which may have a, more preferably substituted It has one or two alkyl groups having 1 to 4 carbon atoms as a group, and -SO 3 - a phenyl group optionally having a, R 47a ~ R 54a is more preferably a hydrogen atom or -SO 3 - is and, R 45a is more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, R 46a is more preferably a substituent has one or two alkyl groups having 1 to 8 carbon atoms, and -SO 3 - one or two carbon atoms 1 to 4 as a phenyl group optionally, even more preferably substituent having a alkyl group, and -SO 3 - a phenyl group optionally having, as well as R 56a is more preferably has one or two halogen atoms as substituents, and -SO 3 - a phenyl group which may have a, more preferably has one or two fluorine atom as a substituent, and -SO 3 - is a phenyl group which may have a.
　化合物（Ａ３－１）の中でも、下記式（Ａ３－１－１）で表される化合物（以下「化合物（Ａ３－１－１）」と記載することがある）が特に好ましい。なお、下記式（Ａ３－１－１）中、二つの「－ＳＯ３ －」の記載は、各アニオンが置換基として－ＳＯ３ －を有し、且つ各アニオン中の－ＳＯ３ －の個数の合計が２（即ち、二つのアニオン中の－ＳＯ３ －の個数の合計が４）であることを意味する。 Among the compounds (A3-1), a compound represented by the following formula (A3-1-1) (hereinafter, may be referred to as “compound (A3-1-1)”) is particularly preferable. In the following formulas (a3-1-1), the two - the description of, -SO 3 as the anion substituent "-SO 3" - has, and -SO 3 in each anion - number of total 2 (i.e., -SO 3 in two anion - total number of 4) meant to be.
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
　化合物（Ａ３－１）は、公知の方法（例えばJournal of Organic Chemistry, (1994), vol. 59, #11, pp. 3232-3236に記載の方法、特開２０１８－１２７５９６号公報に記載の方法）に準じて製造することができる。 The compound (A3-1) is a known method (for example, the method described in Journal of Organic Chemistry, (1994), vol. 59, # 11, pp. 3232-3236, the method described in JP-A-2018-127596. ) Can be manufactured.
　次に、式（Ａ３－２）中の基等について説明する。
　式（Ａ３－２）中のＲ４１ｂおよびＲ４２ｂは、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１～２０の飽和炭化水素基、置換基を有していてもよい炭素数６～１４の芳香族炭化水素基、または置換基を有していてもよい炭素数７～３０のアラルキル基を表すか、或いはＲ４１ｂとＲ４２ｂとが結合して、それらが結合する窒素原子と共に３～１０員の含窒素複素環を形成する。 Next, the groups and the like in the formula (A3-2) will be described.
R 41b and R 42b in the formula (A3-2) each independently have a hydrogen atom and a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent which may have a substituent. It represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R 41b and R 42b are bonded to each other. It forms a 3- to 10-membered nitrogen-containing heterocycle with the bonding nitrogen atom.
　式（Ａ３－２）中の炭素数１～２０の飽和炭化水素基が有していてもよい置換基は、ハロゲン原子、ヒドロキシ基、ホルミル基およびアミノ基からなる群から選ばれる少なくとも一つである。 The substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (A3-2) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group. is there.
　式（Ａ３－２）中の炭素数１～２０の飽和炭化水素基が炭素数２～２０の飽和炭化水素基である場合、前記飽和炭化水素基に含まれる－ＣＨ２－は、－Ｏ－または－ＣＯ－に置き換わっていてもよい。ここで前記－ＣＨ２－には、窒素原子と結合している－ＣＨ２－および前記飽和炭化水素基の末端であるメチル基中の－ＣＨ２－は含まれない。また、前記飽和炭化水素基に含まれる－ＣＨ２－ＣＨ２－が、－Ｏ－Ｏ－または－ＣＯ－ＣＯ－に置き換わることはない。 When the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (A3-2) is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH 2- contained in the saturated hydrocarbon group is -O-. Alternatively, it may be replaced with -CO-. Here, -CH 2- does not include -CH 2 -bonded to a nitrogen atom and -CH 2- in the methyl group at the end of the saturated hydrocarbon group. Further, -CH 2- CH 2- contained in the saturated hydrocarbon group is not replaced with -O-O- or -CO-CO-.
　式（Ａ３－２）中の炭素数６～１４の芳香族炭化水素基が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つである。 The substituent which the aromatic hydrocarbon group having 6 to 14 carbon atoms in the formula (A3-2) may have has a halogen atom, a nitro group, a hydroxy group, a formyl group, and a substituent. It is at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms.
　式（Ａ３－２）中の炭素数７～３０のアラルキル基が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つである。 The substituent which may have an aralkyl group having 7 to 30 carbon atoms in the formula (A3-2) is a halogen atom, a nitro group, a hydroxy group, a formyl group, and a carbon which may have a substituent. It is at least one selected from the group consisting of alkyl groups of numbers 1-8.
　式（Ａ３－２）中の炭素数１～８のアルキル基が有していてもよい置換基は、ハロゲン原子、ヒドロキシ基、ホルミル基およびアミノ基からなる群から選ばれる少なくとも一つである。 The substituent that the alkyl group having 1 to 8 carbon atoms in the formula (A3-2) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
　式（Ａ３－２）中の炭素数１～８のアルキル基が炭素数２～８のアルキル基である場合、前記アルキル基に含まれる－ＣＨ２－は、－Ｏ－または－ＣＯ－に置き換わっていてもよい。ここで前記－ＣＨ２－には、前記アルキル基の末端であるメチル基中の－ＣＨ２－は含まれない。また、前記アルキル基に含まれる－ＣＨ２－ＣＨ２－が、－Ｏ－Ｏ－または－ＣＯ－ＣＯ－に置き換わることはない。 When the alkyl group having 1 to 8 carbon atoms in the formula (A3-2) is an alkyl group having 2 to 8 carbon atoms, -CH 2- contained in the alkyl group is replaced with -O- or -CO-. May be. Wherein the -CH 2 - The, -CH 2 in a methyl group is the terminal of the alkyl group - is not included. Further, -CH 2- CH 2- contained in the alkyl group is not replaced with -OO- or -CO-CO-.
　Ｒ４１ｂは、好ましくは水素原子または炭素数１～８のアルキル基、より好ましくは水素原子または炭素数１～４のアルキル基、さらに好ましくは炭素数１～４のアルキル基である。
　Ｒ４２ｂは、好ましくは炭素数１～８のアルキル基を有していてもよいフェニル基、より好ましくは炭素数１～４のアルキル基を有していてもよいフェニル基、さらに好ましくはフェニル基である。 R 41b is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms.
R 42b preferably has a phenyl group which may have an alkyl group having 1 to 8 carbon atoms, more preferably a phenyl group which may have an alkyl group having 1 to 4 carbon atoms, and further preferably a phenyl group. Is.
　式（Ａ３－２）中のＲ４３ｂおよびＲ４４ｂは、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１～２０の飽和炭化水素基、置換基を有していてもよい炭素数６～１４の芳香族炭化水素基、または置換基を有していてもよい炭素数７～３０のアラルキル基を表すか、或いはＲ４３ｂとＲ４４ｂとが結合してそれらが結合する窒素原子と共に３～１０員の含窒素複素環を形成する。 R 43b and R 44b in the formula (A3-2) each independently have a hydrogen atom and a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and a substituent. It represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R 43b and R 44b are bonded to each other. It forms a 3- to 10-membered nitrogen-containing heterocycle with the nitrogen atom.
　Ｒ４３ｂは、好ましくは水素原子または炭素数１～８のアルキル基、より好ましくは水素原子または炭素数１～４のアルキル基、さらに好ましくは炭素数１～４のアルキル基である。
　Ｒ４４ｂは、好ましくは炭素数１～８のアルキル基を有していてもよいフェニル基、より好ましくは炭素数１～４のアルキル基を有していてもよいフェニル基、さらに好ましくはフェニル基である。 R 43b is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms.
R 44b preferably has a phenyl group having 1 to 8 carbon atoms, more preferably a phenyl group having 1 to 4 carbon atoms, and even more preferably a phenyl group. Is.
　式（Ａ３－２）中のＲ４７ｂ～Ｒ５４ｂは、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、ヒドロキシ基、または置換基を有していてもよい炭素数１～８のアルキル基を表す。 R 47b to R 54b in the formula (A3-2) are alkyl groups having 1 to 8 carbon atoms, which may independently have a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or a substituent. Represents.
　Ｒ４７ｂ～Ｒ５４ｂは、それぞれ独立して、好ましくは水素原子または炭素数１～８のアルキル基、より好ましくは水素原子または炭素数１～４のアルキル基、さらに好ましくは水素原子である。 Each of R 47b to R 54b is independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom.
　式（Ａ３－２）中の環Ｔ１ｂは、置換基を有していてもよい炭素数６～１４の芳香族炭化水素環または置換基を有していてもよい５～１０員の芳香族複素環を表す。 The ring T 1b in the formula (A3-2) may have an aromatic hydrocarbon ring having 6 to 14 carbon atoms which may have a substituent or a 5- to 10-membered aromatic which may have a substituent. Represents a heterocycle.
　式（Ａ３－２）中の炭素数６～１４の芳香族炭化水素環が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つである。 The substituent which the aromatic hydrocarbon ring having 6 to 14 carbon atoms in the formula (A3-2) may have has a halogen atom, a nitro group, a hydroxy group, a formyl group, and a substituent. It is at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms.
　式（Ａ３－２）中の５～１０員の芳香族複素環が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つである。 The substituent which the 5- to 10-membered aromatic heterocycle in the formula (A3-2) may have may have a halogen atom, a nitro group, a hydroxy group, a formyl group, and a substituent. It is at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms.
　環Ｔ１ｂは、好ましくは式（２ｔ）： Ring T 1b is preferably of formula (2t):
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
で表される環である。
　式（２ｔ）中のＲ４５ｂおよびＲ４６ｂは、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１～２０の飽和炭化水素基、置換基を有していてもよい炭素数６～１４の芳香族炭化水素基、または置換基を有していてもよい炭素数７～３０のアラルキル基を表すか、或いはＲ４５ｂとＲ４６ｂとが結合して、それらが結合する窒素原子と共に３～１０員の含窒素複素環を形成する。 It is a ring represented by.
R 45b and R 46b in the formula (2t) may independently have a hydrogen atom and a substituent and may have a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent. It represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R 45b and R 46b are bonded to each other. It forms a 3- to 10-membered nitrogen-containing heterocycle with a nitrogen atom.
　式（２ｔ）中の炭素数１～２０の飽和炭化水素基が有していてもよい置換基は、ハロゲン原子、ヒドロキシ基、ホルミル基およびアミノ基からなる群から選ばれる少なくとも一つである。 The substituent that the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (2t) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
　式（２ｔ）中の炭素数６～１４の芳香族炭化水素基が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つである。 The substituent which the aromatic hydrocarbon group having 6 to 14 carbon atoms in the formula (2t) may have may have a halogen atom, a nitro group, a hydroxy group, a formyl group and a carbon which may have a substituent. It is at least one selected from the group consisting of alkyl groups of numbers 1-8.
　式（２ｔ）中の炭素数７～３０のアラルキル基が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つである。 The substituent which may have an aralkyl group having 7 to 30 carbon atoms in the formula (2t) may have a halogen atom, a nitro group, a hydroxy group, a formyl group and a substituent having 1 to 1 carbon atoms. At least one selected from the group consisting of 8 alkyl groups.
　式（２ｔ）中の炭素数１～８のアルキル基が有していてもよい置換基は、ハロゲン原子、ヒドロキシ基、ホルミル基およびアミノ基からなる群から選ばれる少なくとも一つである。 The substituent that the alkyl group having 1 to 8 carbon atoms in the formula (2t) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
　Ｒ４５ｂは、好ましくは水素原子または炭素数１～８のアルキル基、より好ましくは水素原子または炭素数１～４のアルキル基、さらに好ましくは炭素数１～４のアルキル基である。 R 45b is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms.
　Ｒ４６ｂは、好ましくは炭素数１～８のアルキル基を有していてもよいフェニル基、より好ましくは置換基として１個または２個の炭素数１～８のアルキル基を有するフェニル基、さらに好ましくは置換基として１個または２個の炭素数１～４のアルキル基を有するフェニル基である。 R 46b is preferably a phenyl group which may have an alkyl group having 1 to 8 carbon atoms, more preferably a phenyl group having 1 or 2 alkyl groups having 1 to 8 carbon atoms as a substituent, and further. It is preferably a phenyl group having one or two alkyl groups having 1 to 4 carbon atoms as a substituent.
　式（２ｔ）中のＲ５６ｂは、水素原子、置換基を有していてもよい炭素数１～２０の飽和炭化水素基、置換基を有していてもよい炭素数６～１４の芳香族炭化水素基、または置換基を有していてもよい炭素数７～３０のアラルキル基を表す。 R 56b in the formula (2t) is a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and an aromatic having 6 to 14 carbon atoms which may have a substituent. Represents an aralkyl group having 7 to 30 carbon atoms which may have a hydrocarbon group or a substituent.
　Ｒ５６ｂは、好ましくはハロゲン原子および炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つの置換基を有していてもよいフェニル基、より好ましくは置換基として１個または２個のハロゲン原子を有するフェニル基、さらに好ましくは置換基として１個または２個のフッ素原子を有するフェニル基である。 R 56b is preferably a phenyl group which may have at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 8 carbon atoms, and more preferably one or two substituents. A phenyl group having a halogen atom, more preferably a phenyl group having one or two fluorine atoms as a substituent.
　式（２ｔ）中のＬ１ｂは、硫黄原子、酸素原子または－ＮＲ５７ｂ－を表す。Ｒ５７ｂは、水素原子または炭素数１～１０のアルキル基を表す。Ｌ１ｂは、好ましくは硫黄原子である。
　式（２ｔ）中の＊は、カルボカチオンとの結合位置を表す。 L 1b in the formula (2t) represents a sulfur atom, an oxygen atom or -NR 57b- . R 57b represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. L 1b is preferably a sulfur atom.
* In the formula (2t) represents the bonding position with the carbocation.
　式（Ａ３－２）中のｍは、１以上の整数を表す。ｍは、好ましくは１～２０の整数、より好ましくは２～１４の整数、さらに好ましくは２～８の整数、特に好ましくは３である。ｍが２以上の整数である場合、式（Ａ３－２ｃ）： M in the formula (A3-2) represents an integer of 1 or more. m is preferably an integer of 1 to 20, more preferably an integer of 2 to 14, still more preferably an integer of 2 to 8, and particularly preferably 3. When m is an integer of 2 or more, the formula (A3-2c):
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
［式（Ａ３－２ｃ）中、環Ｔ１ｂ、Ｒ４１ｂ～Ｒ４４ｂおよびＲ４７ｂ～Ｒ５４ｂは、それぞれ、上記と同義である。］
で表される複数のカチオンは、同一でも、異なっていてもよい。式（Ａ３－２ｃ）で表されるカチオンを、以下「カチオン（Ａ３－２ｃ）」と記載することがある。複数のカチオン（Ａ３－２ｃ）は、同一であることが好ましい。 [In the formula (A3-2c), rings T 1b , R 41b to R 44b and R 47b to R 54b are synonymous with the above, respectively. ]
The plurality of cations represented by may be the same or different. The cation represented by the formula (A3-2c) may be hereinafter referred to as "cation (A3-2c)". The plurality of cations (A3-2c) are preferably the same.
　式（Ａ３－２）中の［Ｙ］ｍ－は、ｍ価のアニオンを表す。［Ｙ］ｍ－は、好ましくはタングステン原子を含有するポリ酸アニオンであり、より好ましくは［ＰＷ１２Ｏ４０］３－、［Ｐ２Ｗ１８Ｏ６２］６－、［Ｐ２Ｗ１８Ｏ６２］６－、［ＳｉＷ１２Ｏ４０］４－、［ＳｉＷ１２Ｏ４０］４－、［ＳｉＷ１２Ｏ４０］４－、［Ｐ２Ｗ１７Ｏ６１］１０－、［Ｐ２Ｗ１５Ｏ５６］１２－、［Ｈ２Ｐ２Ｗ１２Ｏ４８］１２－、［ＮａＰ５Ｗ３０Ｏ１１０］１４－、［ＳｉＷ９Ｏ３４］１０－、［ＳｉＷ１０Ｏ３６］８－、［ＳｉＷ１１Ｏ３９］８－、［ＳｉＷ１１Ｏ３９］８－、［Ｗ６Ｏ１９］２－、［Ｗ１０Ｏ３２］４－または［ＷＯ４］２－であり、さらに好ましくは［ＰＷ１２Ｏ４０］３－である。 [Y] m- in the formula (A3-2) represents an m-valent anion. [Y] m- is preferably a polyacid anion containing a tungsten atom, more preferably [PW 12 O 40 ] 3- , [P 2 W 18 O 62 ] 6- , [P 2 W 18 O 62]. ] 6- , [SiW 12 O 40 ] 4- , [SiW 12 O 40 ] 4- , [SiW 12 O 40 ] 4- , [P 2 W 17 O 61 ] 10- , [P 2 W 15 O 56 ] 12- , [H 2 P 2 W 12 O 48 ] 12- , [NaP 5 W 30 O 110 ] 14- , [SiW 9 O 34 ] 10- , [SiW 10 O 36 ] 8- , [SiW 11 O 39] ] 8- , [SiW 11 O 39 ] 8- , [W 6 O 19 ] 2- , [W 10 O 32 ] 4- or [WO 4 ] 2- , more preferably [PW 12 O 40 ] 3 - .
　化合物（Ａ３－２）としては、
　Ｒ４１ｂ、Ｒ４３ｂおよびＲ４７ｂ～Ｒ５４ｂが、それぞれ独立して、水素原子または炭素数１～８のアルキル基であり、
　Ｒ４２ｂおよびＲ４４ｂが、それぞれ独立して、炭素数１～８のアルキル基を有していてもよいフェニル基であり、
　環Ｔ１ｂが、式（２ｔ）で表される環であり［式（２ｔ）中、Ｒ４５ｂが、水素原子または炭素数１～８のアルキル基であり、
　Ｒ４６ｂが、炭素数１～８のアルキル基を有していてもよいフェニル基であり、
　Ｒ５６ｂが、ハロゲン原子および炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つの置換基を有していてもよいフェニル基であり、
　Ｌ１ｂが、硫黄原子であり、並びに
　＊は、カルボカチオンとの結合位置を表す。］、
　ｍが、３であり、
　三つのカチオン（Ａ３－２ｃ）が、同一であり、並びに
　［Ｙ］ｍ－が、［ＰＷ１２Ｏ４０］３－である
化合物（以下「化合物（Ａ３－２’）」と記載することがある）が好ましい。 As a compound (A3-2),
R 41b , R 43b and R 47b to R 54b are independently hydrogen atoms or alkyl groups having 1 to 8 carbon atoms.
R 42b and R 44b are phenyl groups which may independently have an alkyl group having 1 to 8 carbon atoms.
Ring T 1b is a ring represented by the formula (2t) [in formula (2t), R 45b is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R 46b is a phenyl group which may have an alkyl group having 1 to 8 carbon atoms.
R 56b is a phenyl group which may have at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 8 carbon atoms.
L 1b is a sulfur atom, and * represents a bond position with a carbocation. ],
m is 3,
A compound in which the three cations (A3-2c) are the same and [Y] m- is [PW 12 O 40 ] 3- (hereinafter sometimes referred to as "compound (A3-2')"). ) Is preferable.
　化合物（Ａ３－２’）において、Ｒ４１ｂおよびＲ４３ｂは、それぞれ独立して、好ましくは水素原子または炭素数１～８のアルキル基、より好ましくは水素原子または炭素数１～４のアルキル基、さらに好ましくは炭素数１～４のアルキル基であり、Ｒ４２ｂおよびＲ４４ｂは、それぞれ独立して、より好ましくは炭素数１～４のアルキル基を有していてもよいフェニル基、さらに好ましくはフェニル基であり、Ｒ４７ｂ～Ｒ５４ｂは、それぞれ独立して、より好ましくは水素原子または炭素数１～４のアルキル基、さらに好ましくは水素原子であり、Ｒ４５ｂは、より好ましくは水素原子または炭素数１～４のアルキル基、さらに好ましくは炭素数１～４のアルキル基であり、Ｒ４６ｂは、より好ましくは置換基として１個または２個の炭素数１～８のアルキル基を有するフェニル基、さらに好ましくは置換基として１個または２個の炭素数１～４のアルキル基を有するフェニル基であり、並びにＲ５６ｂは、より好ましくは置換基として１個または２個のハロゲン原子を有するフェニル基、さらに好ましくは置換基として１個または２個のフッ素原子を有するフェニル基である。 In the compound (A3-2'), R 41b and R 43b are independently, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having a hydrogen atom or 1 to 4 carbon atoms. More preferably, it is an alkyl group having 1 to 4 carbon atoms, and R 42b and R 44b are independent phenyl groups, more preferably having an alkyl group having 1 to 4 carbon atoms, more preferably. It is a phenyl group, and R 47b to R 54b are independently, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably a hydrogen atom, and R 45b is more preferably a hydrogen atom or An alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and R 46b more preferably a phenyl having one or two alkyl groups having 1 to 8 carbon atoms as a substituent. A group, more preferably a phenyl group having one or two alkyl groups having 1 to 4 carbon atoms as a substituent, and R 56b more preferably having one or two halogen atoms as a substituent. It is a phenyl group, more preferably a phenyl group having one or two fluorine atoms as a substituent.
　化合物（Ａ３－２）の中でも、下記式（Ａ３－２－１）で表される化合物（以下「化合物（Ａ３－２－１）」と記載することがある）が特に好ましい。 Among the compounds (A3-2), a compound represented by the following formula (A3-2-1) (hereinafter sometimes referred to as "compound (A3-2-1)") is particularly preferable.
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
　化合物（Ａ３－２）は、公知の方法（例えば、特開２０１５－２８１２１号公報に記載の方法）に準じて製造することができる。 The compound (A3-2) can be produced according to a known method (for example, the method described in JP-A-2015-28121).
　化合物（Ａ３）は、これを溶かさない溶剤と混合して、化合物（Ａ３）の分散液として用いることが好ましい。化合物（Ａ３）の分散液を製造する際には、分散剤を使用することが好ましい。分散剤としては、例えば、顔料分散液のために上述したものが挙げられる。 It is preferable that the compound (A3) is mixed with a solvent that does not dissolve the compound (A3) and used as a dispersion liquid of the compound (A3). When producing the dispersion liquid of the compound (A3), it is preferable to use a dispersant. Dispersants include, for example, those described above for pigment dispersions.
　化合物（Ａ３）の分散液に分散剤が含まれる場合、その含有量は、化合物（Ａ３）１００重量部に対して、好ましくは１重量部以上５００重量部以下であり、より好ましくは５重量部以上３００重量部以下である。分散剤の含有量が前記の範囲内にあると、均一な分散状態の顔料分散液が得られる傾向がある。 When the dispersion of compound (A3) contains a dispersant, the content thereof is preferably 1 part by weight or more and 500 parts by weight or less, more preferably 5 parts by weight, based on 100 parts by weight of compound (A3). More than 300 parts by weight or less. When the content of the dispersant is within the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.
　化合物（Ａ３）を使用する場合、その含有量は、固形分の総量に対して、１重量％以上であることが好ましく、１．５重量％以上であることがより好ましく、６０重量％以下であることが好ましく、５５重量％以下であることがより好ましく、５０重量％以下であることがさらに好ましい。 When compound (A3) is used, its content is preferably 1% by weight or more, more preferably 1.5% by weight or more, and 60% by weight or less, based on the total amount of solids. It is preferably 55% by weight or less, and further preferably 50% by weight or less.
　化合物（Ａ３）を使用する場合、化合物（Ａ３）とは異なる染料（Ａ１）を使用することが好ましい。即ち、本発明の好ましい一態様では、着色剤（Ａ）が、化合物（Ａ３）とは異なる染料（Ａ１）および化合物（Ａ３）を含む。この一態様における染料（Ａ１）の種類および含有量等の説明は、上述の通りである。 When the compound (A3) is used, it is preferable to use a dye (A1) different from the compound (A3). That is, in a preferred embodiment of the present invention, the colorant (A) contains a dye (A1) and a compound (A3) different from the compound (A3). The description of the type and content of the dye (A1) in this aspect is as described above.
　染料（Ａ１）および化合物（Ａ３）を使用する場合、染料（Ａ１）と化合物（Ａ３）との重量比（染料（Ａ１）：化合物（Ａ３））は、好ましくは０．５：９９．５～９９：１であり、より好ましくは０．５：９９．５～９５：５であり、特に好ましくは０．５：９５～９０：１０である。 When the dye (A1) and the compound (A3) are used, the weight ratio of the dye (A1) to the compound (A3) (dye (A1): compound (A3)) is preferably 0.5: 99.5 to. It is 99: 1, more preferably 0.5: 99.5 to 95: 5, and particularly preferably 0.5: 95 to 90:10.
＜樹脂（Ｂ）＞
　本発明で使用する樹脂（Ｂ）は、式（１ｂ）： <Resin (B)>
The resin (B) used in the present invention has the formula (1b):
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
［式（１ｂ）中、Ｒ１Ｂは、水素原子またはメチル基を表し、
　Ｒ２Ｂ～Ｒ４Ｂは、それぞれ独立に、水素原子、炭素数１～６のアルキル基または炭素数１～６のアルコキシ基を表し、
　ｎは、１～１０の整数を表し、および
　＊は、結合位置を表し、
　但し、Ｒ２Ｂ～Ｒ４Ｂの少なくとも一つは、炭素数１～６のアルコキシ基である。］
で表される構成単位（ｂ１－１）（以下「構成単位（ｂ１－１）」と記載することがある）を含む樹脂（Ｂ１）を含む。樹脂（Ｂ１）中、構成単位（ｂ１－１）は、１種のみが含まれていてもよく、２種以上が含まれていてもよい。樹脂（Ｂ１）を使用することによって、加熱（特にポストベーク）による着色パターンまたは着色塗膜の厚さの減少を抑制することができる。 [In formula (1b), R 1B represents a hydrogen atom or a methyl group.
R 2B to R 4B independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
n represents an integer from 1 to 10, and * represents the bond position.
However, at least one of R 2B to R 4B is an alkoxy group having 1 to 6 carbon atoms. ]
Includes a resin (B1) containing a structural unit (b1-1) represented by (hereinafter, may be referred to as “constituent unit (b1-1)”). In the resin (B1), the constituent unit (b1-1) may contain only one type, or may contain two or more types. By using the resin (B1), it is possible to suppress a decrease in the thickness of the colored pattern or the colored coating film due to heating (particularly post-baking).
　Ｒ２Ｂ～Ｒ４Ｂにおける炭素数１～６のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、イソプロピル基、イソブチル基、イソペンチル基、ネオペンチル基が挙げられる。 Examples of the alkyl group having 1 to 6 carbon atoms in R 2B to R 4B include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, an isopentyl group and a neopentyl group. Be done.
　Ｒ２Ｂ～Ｒ４Ｂにおける炭素数１～６のアルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、イソプロポキシ基、イソブトキシ基、イソペンチルオキシ基、ネオペンチルオキシ基が挙げられる。 Examples of the alkoxy group having 1 to 6 carbon atoms in R 2B to R 4B include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an isopropoxy group, an isobutoxy group and an isopentyloxy group. , Neopentyloxy group.
　Ｒ２Ｂ～Ｒ４Ｂは、それぞれ独立に、好ましくはメトキシ基、エトキシ基またはプロポキシ基、より好ましくはメトキシ基またはエトキシ基である。
　ｎは、好ましくは１～６の整数、より好ましくは１～３の整数である。 R 2B to R 4B are independently, preferably a methoxy group, an ethoxy group or a propoxy group, and more preferably a methoxy group or an ethoxy group.
n is preferably an integer of 1 to 6, and more preferably an integer of 1 to 3.
　樹脂（Ｂ１）は、好ましくは構成単位（ｂ１－１）、酸性基を有する重合性不飽和化合物に由来する構成単位（ｂ１－２）（以下「構成単位（ｂ１－２）」と記載することがある）および他の構成単位（ｂ１－３）（以下「構成単位（ｂ１－３）」と記載することがある）を含む共重合体である。ここで、他の構成単位（ｂ１－３）とは、構成単位（ｂ１－１）および構成単位（ｂ１－２）とは異なる構成単位を意味する。共重合体である樹脂（Ｂ１）中、構成単位（ｂ１－１）、構成単位（ｂ１－２）および構成単位（ｂ１－３）は、いずれも、１種のみが含まれていてもよく、２種以上が含まれていてもよい。 The resin (B1) is preferably described as a structural unit (b1-1), a structural unit (b1-2) derived from a polymerizable unsaturated compound having an acidic group (hereinafter, “constituent unit (b1-2)”). (There is) and other structural units (b1-3) (hereinafter sometimes referred to as "constituent units (b1-3)"). Here, the other structural unit (b1-3) means a structural unit different from the structural unit (b1-1) and the structural unit (b1-2). In the resin (B1) which is a copolymer, only one kind of the structural unit (b1-1), the structural unit (b1-2) and the structural unit (b1-3) may be contained. Two or more types may be included.
　構成単位（ｂ１－２）が有する酸性基としては、例えば、カルボキシ基、リン酸基（－Ｏ－Ｐ（＝Ｏ）（ＯＨ）２）、スルホ基（－Ｓ（＝Ｏ）２ＯＨ）が挙げられる。これらの中で、カルボキシ基が好ましい。 Examples of the acidic group contained in the structural unit (b1-2) include a carboxy group, a phosphoric acid group (-OP (= O) (OH) 2 ), and a sulfo group (-S (= O) 2 OH). Can be mentioned. Of these, a carboxy group is preferred.
　共重合体中の全構成単位の合計を１００モル％としたときの構成単位（ｂ１－１）の量は、耐溶剤性の観点から、好ましくは１～５０モル％、より好ましくは５～４０モル％、さらに好ましくは１０～３０モル％である。 The amount of the structural unit (b1-1) when the total of all the structural units in the copolymer is 100 mol% is preferably 1 to 50 mol%, more preferably 5 to 40, from the viewpoint of solvent resistance. It is mol%, more preferably 10 to 30 mol%.
　共重合体中の全構成単位の合計を１００モル％としたときの構成単位（ｂ１－２）の量は、現像性の観点から、好ましくは１０～５０モル％、より好ましくは１５～４５モル％、さらに好ましくは２０～４０モル％である。 The amount of the structural unit (b1-2) when the total of all the structural units in the copolymer is 100 mol% is preferably 10 to 50 mol%, more preferably 15 to 45 mol, from the viewpoint of developability. %, More preferably 20-40 mol%.
　共重合体中の全構成単位の合計を１００モル％としたときの構成単位（ｂ１－３）の量は、現像性および耐溶剤性の観点から、好ましくは１～８９モル％、より好ましくは１５～８０モル％、さらに好ましくは３０～７０モル％である。 The amount of the structural units (b1-3) when the total of all the structural units in the copolymer is 100 mol% is preferably 1 to 89 mol%, more preferably 1 to 89 mol%, from the viewpoint of developability and solvent resistance. It is 15 to 80 mol%, more preferably 30 to 70 mol%.
　樹脂（Ｂ１）の重量平均分子量（Ｍｗ）は、現像性の観点から、１，０００～５０，０００、好ましくは２，０００～４０，０００であり、より好ましくは３，０００～３０，０００である。前記重量平均分子量（Ｍｗ）は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）を用いて、ポリスチレン換算にて算出される値である。 The weight average molecular weight (Mw) of the resin (B1) is 1,000 to 50,000, preferably 2,000 to 40,000, and more preferably 3,000 to 30,000 from the viewpoint of developability. is there. The weight average molecular weight (Mw) is a value calculated in terms of polystyrene using gel permeation chromatography (GPC).
　樹脂（Ｂ１）のシリル基当量は、耐熱分解性、耐熱黄変性および耐溶剤性の観点から、好ましくは４００～４，０００、より好ましくは５００～３，０００である。樹脂（Ｂ１）のシリル基当量が４００以上であれば、着色パターンまたは着色塗膜の耐熱分解性および耐熱黄変性をより高めるのに効果的である。なお、樹脂（Ｂ１）のシリル基当量は、下記式：
　シリル基当量＝樹脂（Ｂ１）の重量平均分子量／１分子当たりのシリル基の平均個数
から算出される値である。シリル基当量は、樹脂（Ｂ１）の製造に使用する単量体の仕込量から算出することができる。 The silyl group equivalent of the resin (B1) is preferably 400 to 4,000, more preferably 500 to 3,000, from the viewpoint of heat-decomposability, heat-resistant yellowing and solvent resistance. When the silyl group equivalent of the resin (B1) is 400 or more, it is effective in further enhancing the heat-resistant decomposition property and heat-resistant yellowing of the colored pattern or the colored coating film. The silyl group equivalent of the resin (B1) is calculated by the following formula:
Cyril group equivalent = a value calculated from the weight average molecular weight of the resin (B1) / the average number of silyl groups per molecule. The silyl group equivalent can be calculated from the amount of the monomer charged in the production of the resin (B1).
　樹脂（Ｂ１）が構成単位（ｂ１－２）を含む共重合体である場合、樹脂（Ｂ１）の酸価は、現像性の観点から、好ましくは２０～３００ｍｇＫＯＨ／ｇ、より好ましくは３０～２００ｍｇＫＯＨ／ｇである。なお、樹脂（Ｂ１）の酸価とは、ＪＩＳ　Ｋ６９０１　５．３に従ってブロモチモールブルーとフェノールレッドの混合指示薬を用いて測定された値であって、樹脂（Ｂ１）１ｇを中和するのに必要な水酸化カリウムの量（ｍｇ）として算出される値であり、例えば水酸化カリウム水溶液を用いて滴定することにより求めることができる。 When the resin (B1) is a copolymer containing a structural unit (b1-2), the acid value of the resin (B1) is preferably 20 to 300 mgKOH / g, more preferably 30 to 200 mgKOH from the viewpoint of developability. / G. The acid value of the resin (B1) is a value measured using a mixed indicator of bromothymol blue and phenol red according to JIS K6901 5.3, and is necessary for neutralizing 1 g of the resin (B1). It is a value calculated as the amount of potassium hydroxide (mg), and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.
　アルカリ現像後に、欠けおよび剥離がない良好なパターンを形成する観点から、樹脂（Ｂ１）の含有量は、重合性化合物（Ｃ）１００重量部に対して、好ましくは５～４００重量部、より好ましくは７．５～３７５重量部、さらに好ましくは１０～３５０重量部である。 The content of the resin (B1) is preferably 5 to 400 parts by weight, more preferably 5 to 400 parts by weight, based on 100 parts by weight of the polymerizable compound (C), from the viewpoint of forming a good pattern without chipping and peeling after alkaline development. Is 7.5 to 375 parts by weight, more preferably 10 to 350 parts by weight.
　樹脂（Ｂ１）は、溶剤の存在下、下記式（２ｂ）： The resin (B1) has the following formula (2b) in the presence of a solvent:
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
［式（２ｂ）中の記号の意味は、上記の通りである］
で表される化合物（ｍ１－１）（以下「化合物（ｍ１－１）」と記載することがある）のみ、または化合物（ｍ１－１）および他の化合物を含むモノマー混合物を、公知のラジカル重合方法に従って共重合させることによって製造することができる。 [The meanings of the symbols in equation (2b) are as described above]
Known radical polymerization of only the compound represented by (m1-1) (hereinafter sometimes referred to as "compound (m1-1)") or a monomer mixture containing the compound (m1-1) and other compounds. It can be produced by copolymerizing according to the method.
　共重合体である樹脂（Ｂ１）は、例えば、化合物（ｍ１－１）および必要に応じて他の化合物を溶剤に溶解して、溶液を調製した後、その溶液に重合開始剤を添加し、５０～１３０℃にて１～２０時間反応させることによって製造することができる。 For the resin (B1) which is a copolymer, for example, a compound (m1-1) and, if necessary, another compound are dissolved in a solvent to prepare a solution, and then a polymerization initiator is added to the solution. It can be produced by reacting at 50 to 130 ° C. for 1 to 20 hours.
　構成単位（ｂ１－１）、構成単位（ｂ１－２）および構成単位（ｂ１－３）を含む共重合体である樹脂（Ｂ１）は、溶剤の存在下、化合物（ｍ１－１）、酸性基を有する重合性不飽和化合物（ｍ１－２）（以下「化合物（ｍ１－２）」と記載することがある）、および他の重合性不飽和化合物（ｍ１－３）（以下「化合物（ｍ１－３）」と記載することがある）からなるモノマー混合物を、公知のラジカル重合方法に従って共重合させることによって製造することができる。ここで、他の重合性不飽和化合物（ｍ１－３）とは、化合物（ｍ１－１）および化合物（ｍ１－２）とは異なる重合性不飽和化合物を意味する。また、構成単位（ｂ１－１）が化合物（ｍ１－１）に由来し、構成単位（ｂ１－２）が化合物（ｍ１－２）に由来し、構成単位（ｂ１－３）が化合物（ｍ１－３）に由来する。 The resin (B1), which is a copolymer containing the structural unit (b1-1), the structural unit (b1-2) and the structural unit (b1-3), is a compound (m1-1) and an acidic group in the presence of a solvent. Polymerizable unsaturated compound (m1-2) (hereinafter sometimes referred to as "compound (m1-2)"), and other polymerizable unsaturated compounds (m1-3) (hereinafter "compound (m1-m1-)"). It can be produced by copolymerizing a monomer mixture consisting of (which may be described as "3)" according to a known radical polymerization method. Here, the other polymerizable unsaturated compound (m1-3) means a polymerizable unsaturated compound different from the compound (m1-1) and the compound (m1-2). Further, the structural unit (b1-1) is derived from the compound (m1-1), the structural unit (b1-2) is derived from the compound (m1-2), and the structural unit (b1-3) is derived from the compound (m1-m1-). Derived from 3).
　共重合体である樹脂（Ｂ１）は、例えば、化合物（ｍ１－１）、化合物（ｍ１－２）および化合物（ｍ１－３）を溶剤に溶解して、溶液を調製した後、その溶液に重合開始剤を添加し、５０～１３０℃にて１～２０時間反応させることによって製造することができる。 The resin (B1), which is a copolymer, is obtained by dissolving, for example, compound (m1-1), compound (m1-2) and compound (m1-3) in a solvent to prepare a solution, and then polymerizing the solution. It can be produced by adding an initiator and reacting at 50 to 130 ° C. for 1 to 20 hours.
　化合物（ｍ１－１）としては、例えば、３－（メタ）アクリロイルオキシプロピルメチルジメトキシシラン、３－（メタ）アクリロイルオキシプロピルエチルジメトキシシラン、３－（メタ）アクリロイルオキシプロピルメチルジエトキシシラン、３－（メタ）アクリロイルオキシプロピルエチルジエトキシシラン、３－（メタ）アクリロイルオキシプロピルトリメトキシシラン、３－（メタ）アクリロイルオキシプロピルトリエトキシシラン等が挙げられる。これらの中で、入手のし易さおよび反応性の観点から、３－（メタ）アクリロイルオキシプロピルトリメトキシシランおよび３－（メタ）アクリロイルオキシプロピルトリエトキシシランが好ましい。ここで「３－（メタ）アクリロイルオキシプロピルメチルジメトキシシラン」とは、３－アクリロイルオキシプロピルメチルジメトキシシランおよび３－メタクリロイルオキシプロピルメチルジメトキシシランから選ばれる少なくとも一つを意味する。他の同様の記載も同様の意味である。 Examples of the compound (m1-1) include 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- Examples thereof include (meth) acryloyloxypropyl ethyldiethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, and 3- (meth) acryloyloxypropyltriethoxysilane. Among these, 3- (meth) acryloyloxypropyltrimethoxysilane and 3- (meth) acryloyloxypropyltriethoxysilane are preferable from the viewpoint of availability and reactivity. Here, "3- (meth) acryloyloxypropylmethyldimethoxysilane" means at least one selected from 3-acryloyloxypropylmethyldimethoxysilane and 3-methacryloyloxypropylmethyldimethoxysilane. Other similar statements have the same meaning.
　化合物（ｍ１－２）が有する酸性基としては、例えば、カルボキシ基、リン酸基（－Ｏ－Ｐ（＝Ｏ）（ＯＨ）２）、スルホ基（－Ｓ（＝Ｏ）２ＯＨ）が挙げられる。これらの中で、カルボキシ基が好ましい。 Examples of the acidic group contained in the compound (m1-2) include a carboxy group, a phosphoric acid group (-OP (= O) (OH) 2 ), and a sulfo group (-S (= O) 2 OH). Be done. Of these, a carboxy group is preferred.
　化合物（ｍ１－２）としては、例えば、（メタ）アクリル酸、クロトン酸、桂皮酸、ビニルスルホン酸、２－（メタ）アクリロイルオキシエチルコハク酸、２－アクリロイルオキシエチルフタル酸、２－（メタ）アクリロイルオキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイルオキシエチルアシッドホスフェート等が挙げられる。これらの中でも、入手のし易さおよび反応性の観点から、（メタ）アクリル酸が好ましい。 Examples of the compound (m1-2) include (meth) acrylic acid, crotonic acid, cinnamic acid, vinyl sulfonic acid, 2- (meth) acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, and 2- (meth). ) Acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl acid phosphate and the like. Among these, (meth) acrylic acid is preferable from the viewpoint of availability and reactivity.
　化合物（ｍ１－３）としては、例えば、以下のものが挙げられる：
　ブタジエン；
　メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ブチル（メタ）アクリルレート、ｓｅｃ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリルレート、ペンチル（メタ）アクリレート、ネオペンチル（メタ）アクリレート、ベンジル（メタ）アクリレート、イソアミル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、ラウリル（メタ）アクリレート、ドデシル（メタ）アクリレート、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、メチルシクロヘキシル（メタ）アクリレート、エチルシクロヘキシル（メタ）アクリレート、１，４－シクロヘキサンジメタノールモノ（メタ）アクリレート、ロジン（メタ）アクリレート、ノルボルニル（メタ）アクリレート、５－メチルノルボルニル（メタ）アクリレート、５－エチルノルボルニル（メタ）アクリレート、アリル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、１，１，１－トリフルオロエチル（メタ）アクリレート、パーフルオロエチル（メタ）アクリレート、パーフルオロ－プロピル（メタ）アクリレート、パーフルオロ－イソプロピル（メタ）アクリレート、トリフェニルメチル（メタ）アクリレート、クミル（メタ）アクリレート、３－（Ｎ，Ｎ－ジメチルアミノ）プロピル（メタ）アクリレート、グリセリロールモノ（メタ）アクリレート、ブタントリオールモノ（メタ）アクリレート、ペンタントリオールモノ（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、ナフタレン（メタ）アクリレート、アントラセン（メタ）アクリレート、２－（２－ビニロキシエトキシ）エチル（メタ）アクリレート、グリシジル（メタ）アクリレート、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート、（３－エチルオキセタン－３－イル）メチル（メタ）アクリレート、２－イソシアナトエチル（メタ）アクリレート、２－イソシアナトプロピル（メタ）アクリレート、３－イソシアナトプロピル（メタ）アクリレート、２－イソシアナト－１－メチルエチル（メタ）アクリレート、２－イソシアナト－１，１－ジメチルエチル（メタ）アクリレート、４－イソシアナトシクロヘキシル（メタ）アクリレート、前記のイソシアナト基を有する（メタ）アクリレート（例えば、２－イソシアナトエチル（メタ）アクリレート）のイソシアナト基をブロック剤を用いてブロック化することによって得られるブロックイソシアナト基を有する（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリレート、Ｎ－ｔｅｒｔ－ブチルアミノエチル（メタ）アクリレート、テトラメチルピペリジル（メタ）アクリレート、ヘキサメチルピペリジル（メタ）アクリレート；
　（メタ）アクリル酸アミド、（メタ）アクリル酸Ｎ，Ｎ－ジメチルアミド、（メタ）アクリル酸Ｎ，Ｎ－ジエチルアミド、（メタ）アクリル酸Ｎ，Ｎ－ジプロピルアミド、（メタ）アクリル酸Ｎ，Ｎ－ジイソプロピルアミド、（メタ）アクリル酸アントラセニルアミド、Ｎ－イソプロピル（メタ）アクリルアミド、（メタ）アクリルモルフォリン、ダイアセトン（メタ）アクリルアミド；
　ノルボルネン（ビシクロ［２．２．１］ヘプト－２－エン）、５－メチルビシクロ［２．２．１］ヘプト－２－エン、５－エチルビシクロ［２．２．１］ヘプト－２－エン、テトラシクロ［４．４．０．１２，５．１７，１０］ドデカ－３－エン、８－メチルテトラシクロ［４．４．０．１２，５．１７，１０］ドデカ－３－エン、８－エチルテトラシクロ［４．４．０．１２，５．１７，１０］ドデカ－３－エン、ジシクロペンタジエン、トリシクロ［５．２．１．０２，６］デカ－８－エン、トリシクロ［５．２．１．０２，６］デカ－３－エン、トリシクロ［４．４．０．１２，５］ウンデカ－３－エン、トリシクロ［６．２．１．０１，８］ウンデカ－９－エン、トリシクロ［６．２．１．０１，８］ウンデカ－４－エン、テトラシクロ［４．４．０．１２，５．１７，１０．０１，６］ドデカ－３－エン、８－メチルテトラシクロ［４．４．０．１２，５．１７，１０．０１，６］ドデカ－３－エン、８－エチリデンテトラシクロ［４．４．０．１２，５．１７，１２］ドデカ－３－エン、８－エチリデンテトラシクロ［４．４．０．１２，５．１７，１０．０１，６］ドデカ－３－エン、ペンタシクロ［６．５．１．１３，６．０２，７．０９，１３］ペンタデカ－４－エン、ペンタシクロ［７．４．０．１２，５．１９，１２．０８，１３］ペンタデカ－３－エン、５－ノルボルネン－２，３－ジカルボン酸無水物、（メタ）アクリル酸アニリド、（メタ）アクリロイルニトリル、アクロレイン、塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン、ビニルピリジン、酢酸ビニル、ビニルトルエン；
　スチレンおよびその誘導体；
　シトラコン酸ジエチル、マレイン酸ジエチル、フマル酸ジエチル、イタコン酸ジエチル；
　無水マレイン酸、無水イタコン酸、無水シトラコン酸。 Examples of the compound (m1-3) include the following:
butadiene;
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylic rate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) ) Acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, benzyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, lauryl ( Meta) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, rosin (Meta) acrylate, norbornyl (meth) acrylate, 5-methylnorbornyl (meth) acrylate, 5-ethylnorbornyl (meth) acrylate, allyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 1,1 , 1-Trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro-propyl (meth) acrylate, perfluoro-isopropyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate , 3- (N, N-dimethylamino) propyl (meth) acrylate, glycerylol mono (meth) acrylate, butanetriol mono (meth) acrylate, pentatriol mono (meth) acrylate, dicyclopentenyl (meth) acrylate, di Cyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, naphthalene (meth) acrylate, anthracene (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, glycidyl (meth) ) Acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate, 2-isocyanatopropyl (meth) acrylate , 3-Isocyanatopropyl (meth) acrylate, 2-Isocyanato-1 -Methylethyl (meth) acrylate, 2-isocyanato-1,1-dimethylethyl (meth) acrylate, 4-isocyanatocyclohexyl (meth) acrylate, the above-mentioned (meth) acrylate having an isocyanato group (for example, 2-isocyanato). (Meta) acrylate having a blocked isocyanato group obtained by blocking the isocyanato group of ethyl (meth) acrylate with a blocking agent, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylamino Ethyl (meth) acrylate, N-tert-butylaminoethyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, hexamethylpiperidyl (meth) acrylate;
(Meta) Acrylic Acid Amide, (Meta) Acrylic Acid N, N-Dimethylamide, (Meta) Acrylic Acid N, N-Diethylamide, (Meta) Acrylic Acid N, N-Dipropylamide, (Meta) Acrylic Acid N, N-diisopropylamide, (meth) acrylic acid anthracenylamide, N-isopropyl (meth) acrylamide, (meth) acrylic morpholine, diacetone (meth) acrylamide;
Norbornene (bicyclo [2.2.1] hept-2-ene), 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene , Tetracyclo [4.4.0.1 2,5 . 1 7, 10 ] Dodeca-3-ene, 8-methyltetracyclo [4.4.0.1 2,5 . 1 7, 10 ] Dodeca-3-ene, 8-ethyltetracyclo [4.4.0.1 2,5 . 17 and 10 ] Dodeca-3-ene, dicyclopentadiene, tricyclo [5.2.1.0 2,6 ] deca-8-ene, tricyclo [5.2.1.0 2,6 ] deca-3 -En, tricyclo [4.4.0.1 2,5 ] undec-3-ene, tricyclo [6.2.1.0 1,8 ] undec-9-ene, tricyclo [6.2.1.0] 1,8 ] Undeca-4-ene, tetracyclo [4.4.0.1 2,5 . 17 and 10 . 0 1,6 ] Dodeca-3-ene, 8-methyltetracyclo [4.4.0.1 2,5 . 17 and 10 . 0 1,6 ] Dodeca-3-ene, 8-ethylidenetetracyclo [4.4.0.1 2,5 . 17 and 12 ] Dodeca-3-ene, 8-ethylidenetetracyclo [4.4.0.1 2,5 . 17 and 10 . 0 1,6 ] Dodeca-3-ene, pentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13] pentadeca-4-ene, pentacyclo [7.4.0.1 2,5. 19 and 12 . 0 8,13] pentadeca-3-ene, 5-norbornene-2,3-dicarboxylic acid anhydride, (meth) anilide acrylic acid, (meth) acryloyl nitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, Vinylidene chloride, vinylpyridine, vinyl acetate, vinyltoluene;
Styrene and its derivatives;
Diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconic acid;
Maleic anhydride, itaconic anhydride, citraconic anhydride.
　入手のし易さおよび反応性の観点から、化合物（ｍ１－３）としては、メチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、グリシジル（メタ）アクリレート、（３－エチルオキセタン－３－イル）メチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリレート、（メタ）アクリル酸Ｎ，Ｎ－ジメチルアミド、（メタ）アクリルモルフォリン、スチレン、ビニルトルエンおよびノルボルネンが好ましく、メチル（メタ）アクリレート、ベンジル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、グリシジル（メタ）アクリレート、（３－エチルオキセタン－３－イル）メチル（メタ）アクリレート、スチレンおよびビニルトルエンがより好ましい。 From the viewpoint of availability and reactivity, the compound (m1-3) includes methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like. Glycidyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, (meth) acrylate N, N-dimethylamide, (meth) acrylic morpho Phosphorus, styrene, vinyltoluene and norbornene are preferred, methyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, glycidyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (3-ethyloxetane-3-yl) methyl ( Meta) Acrylate, styrene and vinyl toluene are more preferred.
　耐熱分解性および耐熱黄変性の観点から、化合物（ｍ１－３）としては、アルキル（メタ）アクリレートが好ましく、メチル（メタ）アクリレート、ベンジル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレートがより好ましい。 From the viewpoint of heat decomposition and heat yellowing, the compound (m1-3) is preferably an alkyl (meth) acrylate, more preferably a methyl (meth) acrylate, a benzyl (meth) acrylate, or a dicyclopentanyl (meth) acrylate. preferable.
　耐溶剤性の観点から、化合物（ｍ１－３）としては、酸性基と反応する官能基（例えば、グリシジル基、オキセタニル基、イソシアナト基、ブロックイソシアナト基）を有する重合性化合物が好ましく、グリシジル（メタ）アクリレート、（３－エチルオキセタン－３－イル）メチルメタクリレートがより好ましい。 From the viewpoint of solvent resistance, the compound (m1-3) is preferably a polymerizable compound having a functional group (for example, glycidyl group, oxetaneyl group, isocyanato group, block isocyanato group) that reacts with an acidic group, and glycidyl (for example). More preferred are meta) acrylates and (3-ethyloxetane-3-yl) methyl methacrylate.
　上述のイソシアナト基のブロックに用いるブロック剤としては、例えば、以下のものが挙げられる：
　ε－カプロラクタム、δ－バレロラクタム、γ－ブチロラクタム、β－プロピオラクタム等のラクタム系ブロック剤；
　メタノール、エタノール、プロパノール、ブタノール、エチレングリコール、メチルセロソルブ、ブチルセロソルブ、メチルカルビトール、ベンジルアルコール、フェニルセロソルブ、フルフリルアルコール、シクロヘキサノール等のアルコール系ブロック剤；
　フェノール、クレゾール、キシレノール、エチルフェノール、ｏ－イソプロピルフェノール、ｐ－ｔｅｒｔ－ブチルフェノール等のブチルフェノール、ｐ－ｔｅｒｔ－オクチルフェノール、ノニルフェノール、ジノニルフェノール、スチレン化フェノール、オキシ安息香酸エステル、チモール、ｐ－ナフトール、ｐ－ニトロフェノール、ｐ－クロロフェノール等のフェノール系ブロック剤；
　マロン酸ジメチル、マロン酸ジエチル、アセト酢酸メチル、アセト酢酸エチル、アセチルアセトン等の活性メチレン系ブロック剤；
　ブチルメルカプタン、チオフェノール、ｔｅｒｔ－ドデシルメルカプタン等のメルカプタン系ブロック剤；
　ジフェニルアミン、フェニルナフチルアミン、アニリン、カルバゾール等のアミン系ブロック剤；
　アセトアニリド、アセトアニシジド、酢酸アミド、ベンズアミド等の酸アミド系ブロック剤；
　コハク酸イミド、マレイン酸イミド等の酸イミド系ブロック剤；
　イミダゾール、２－メチルイミダゾール、２－エチルイミダゾール等のイミダゾール系ブロック剤；
　尿素、チオ尿素、エチレン尿素等の尿素系ブロック剤；
　Ｎ－フェニルカルバミン酸フェニル、２－オキサゾリドン等のカルバミド酸塩系ブロック剤；
　エチレンイミン、ポリエチレンイミン等のイミン系ブロック剤；
　ホルムアルドオキシム、アセトアルドオキシム、アセトオキシム、メチルエチルケトオキシム、メチルイソブチルケトオキシム、シクロヘキサノンオキシム等のオキシム系ブロック剤；
　重亜硫酸ソーダ、重亜硫酸カリウム等の重亜硫酸塩系ブロック剤。 Examples of the blocking agent used for blocking the above-mentioned isocyanato group include the following:
Lactam-based blocking agents such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam;
Alcohol-based blocking agents such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, cyclohexanol;
Butylphenol such as phenol, cresol, xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, oxybenzoic acid ester, timole, p-naphthol, p. -Phenol-based blocking agents such as nitrophenol and p-chlorophenol;
Active methylene block agents such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone;
Mercaptan-based blocking agents such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan;
Amine-based blocking agents such as diphenylamine, phenylnaphthylamine, aniline, and carbazole;
Acid amide blocking agents such as acetanilide, acetanilide, acetate amide, benzamide;
Acid-imide-based blocking agents such as succinate imide and maleate imide;
Imidazole-based blocking agents such as imidazole, 2-methylimidazole, and 2-ethylimidazole;
Urea-based blocking agents such as urea, thiourea, and ethylene urea;
Carbamide-based blocking agents such as phenyl N-phenylcarbamate and 2-oxazolidone;
Imine-based blocking agents such as ethyleneimine and polyethyleneimine;
Oxime-based blocking agents such as formaldehyde, acetoaldoxime, acetooxime, methylethylketooxime, methylisobutylketooxime, cyclohexanoneoxime;
Sodium bisulfite, potassium bisulfite and other bisulfite-based blocking agents.
　樹脂（Ｂ１）の重量分子量（Ｍｗ）および分子量分布（Ｍｗ／Ｍｎ）を好ましい範囲内に制御するため、および重合時のゲル化を抑制するために、前記重合に用いる溶剤は、炭素数３～１０のヒドロキシ基含有溶剤を含むことが好ましい。炭素数３～１０のヒドロキシ基含有溶剤としては、例えば、プロピルアルコール、ブチルアルコール、ペンチルアルコール、ヘキシルアルコール、オクチルアルコール、ノニルアルコール、デシルアルコール、ベンジルアルコール等のモノアルコール類；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノブチルエーテル、トリプロピレングリコールモノメチルエーテル等の（ポリ）アルキレングリコールモノアルキルエーテル類が挙げられる。 In order to control the weight molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the resin (B1) within a preferable range and to suppress gelation during polymerization, the solvent used for the polymerization has 3 to 3 carbon atoms. It preferably contains 10 hydroxy group-containing solvents. Examples of the hydroxy group-containing solvent having 3 to 10 carbon atoms include monoalcohols such as propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol and benzyl alcohol; ethylene glycol monomethyl ether and ethylene. Glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol Examples thereof include (poly) alkylene glycol monoalkyl ethers such as monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether and tripropylene glycol monomethyl ether.
　前記重合に用いる溶剤は、炭素数３～１０のヒドロキシ基含有溶剤以外の溶剤を含んでいてもよい。前記溶剤としては、例えば、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等の（ポリ）アルキレングリコールモノアルキルエーテルアセテート類；ジエチレングリコールジメチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールジエチルエーテル、テトラヒドロフラン等のエーテル類；メチルエチルケトン、シクロヘキサノン、２－ヘプタノン、３－ヘプタノン等のケトン類；３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、３－メチル－３－メトキシブチルアセテート、３－メチル－３－メトキシブチルプロピオネート、酢酸エチル、酢酸ブチル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、酢酸イソブチル、酢酸アミル、酢酸イソアミル、プロピオン酸ブチル、酪酸エチル、酪酸プロピル、酪酸イソプロピル、酪酸ブチル、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソ酪酸エチル等のエステル類；トルエン、キシレン等の芳香族炭化水素類；Ｎ－メチルピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド等のカルボン酸アミド類等が挙げられる。これらの中でも、反応性の観点から、（ポリ）アルキレングリコールモノアルキルエーテルアセテート類が好ましい。 The solvent used for the polymerization may contain a solvent other than the hydroxy group-containing solvent having 3 to 10 carbon atoms. Examples of the solvent include (poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether and diethylene glycol methyl. Ethers such as ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, butyl acetate, propyl acetate, isopropyl acetate, acetic acid Butyl, isobutyl acetate, amyl acetate, isoamyl acetate, butyl propionate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, 2-oxo Esters such as ethyl butyrate; aromatic hydrocarbons such as toluene and xylene; carboxylic acid amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like can be mentioned. Among these, (poly) alkylene glycol monoalkyl ether acetates are preferable from the viewpoint of reactivity.
　前記重合に用いる溶剤全体に対する炭素数３～１０のヒドロキシ基含有溶剤の含有量は、樹脂（Ｂ１）の重量分子量および分子量分布（Ｍｗ／Ｍｎ）の制御の観点から、１０～１００重量％であることが好ましく、２０～１００重量％であることがより好ましい。 The content of the hydroxy group-containing solvent having 3 to 10 carbon atoms with respect to the entire solvent used for the polymerization is 10 to 100% by weight from the viewpoint of controlling the weight molecular weight and the molecular weight distribution (Mw / Mn) of the resin (B1). It is preferably 20 to 100% by weight, and more preferably 20 to 100% by weight.
　前記重合における溶剤の使用量は、特に限定されないが、化合物（ｍ１－１）、化合物（ｍ１－２）および化合物（ｍ１－３）の使用量の合計１００重量部に対して、好ましくは３０～１，０００重量部、より好ましくは５０～８００重量部である。 The amount of the solvent used in the polymerization is not particularly limited, but is preferably 30 to 30 parts by weight based on 100 parts by weight of the total amount of the compound (m1-1), the compound (m1-2) and the compound (m1-3). It is 1,000 parts by weight, more preferably 50 to 800 parts by weight.
　前記重合に使用し得る重合開始剤としては、特に限定されないが、例えば、２，２’－アゾビス（イソブチロニトリル）、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、２，２’－アゾビス（イソ酪酸）ジメチル、過酸化ベンゾイル、ｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエート等が挙げられる。重合開始剤の使用量は、特に限定されないが、化合物（ｍ１－１）、化合物（ｍ１－２）および化合物（ｍ１－３）の使用量の合計１００重量部に対して、好ましくは０．５～２０重量部、より好ましくは１．０～１０重量部である。 The polymerization initiator that can be used for the polymerization is not particularly limited, and is, for example, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2, Examples thereof include 2'-azobis (isobutyric acid) dimethyl, benzoyl peroxide, and tert-butylperoxy-2-ethylhexanoate. The amount of the polymerization initiator used is not particularly limited, but is preferably 0.5 with respect to 100 parts by weight of the total amount of the compound (m1-1), the compound (m1-2) and the compound (m1-3) used. It is ~ 20 parts by weight, more preferably 1.0 to 10 parts by weight.
　樹脂（Ｂ１）は、好ましくは（メタ）アクリル酸、３－（メタ）アクリロイルオキシプロピルトリメトキシシランおよびメチル（メタ）アクリレートの共重合体である。化合物（Ａ３）を使用する場合は、樹脂（Ｂ１）は、好ましくは（メタ）アクリル酸、３－（メタ）アクリロイルオキシプロピルトリエトキシシランおよびジシクロペンタニル（メタ）アクリレートの共重合体である。 The resin (B1) is preferably a copolymer of (meth) acrylic acid, 3- (meth) acryloyloxypropyltrimethoxysilane and methyl (meth) acrylate. When compound (A3) is used, the resin (B1) is preferably a copolymer of (meth) acrylic acid, 3- (meth) acryloyloxypropyltriethoxysilane and dicyclopentanyl (meth) acrylate. ..
　樹脂（Ｂ）は、樹脂（Ｂ１）とは異なる樹脂（Ｂ２）を含有していてもよい。樹脂（Ｂ２）は、アルカリ可溶性樹脂であることが好ましく、不飽和カルボン酸および不飽和カルボン酸無水物からなる群から選ばれる少なくとも一つの単量体（以下「単量体（ｍ２－１）」と記載することがある）に由来する構成単位を含む重合体であることが好ましい。前記重合体中、前記構成単位は、１種のみが含まれていてもよく、２種以上が含まれていてもよい。 The resin (B) may contain a resin (B2) different from the resin (B1). The resin (B2) is preferably an alkali-soluble resin, and is at least one monomer selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter, "monomer (m2-1)"). It is preferable that the polymer contains a structural unit derived from (may be described as). In the polymer, the structural unit may contain only one type, or may contain two or more types.
　樹脂（Ｂ２）は、単量体（ｍ２－１）に由来する構成単位および炭素数２～４の環状エーテル構造とエチレン性不飽和結合とを有する単量体（以下「単量体（ｍ２－２）」と記載することがある）に由来する構成単位を含む共重合体であることがより好ましい。前記共重合体は、その他の構成単位を含んでいてもよい。その他の構成単位としては、例えば、単量体（ｍ２－１）および単量体（ｍ２－２）とは異なる単量体（以下「単量体（ｍ２－３）」と記載することがある）に由来する構成単位、エチレン性不飽和結合を有する構成単位等が挙げられる。共重合体中、前記構成単位は、いずれも、１種のみが含まれていてもよく、２種以上が含まれていてもよい。 The resin (B2) is a monomer having a structural unit derived from the monomer (m2-1), a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond (hereinafter, “monomer (m2-)”. It is more preferable that the copolymer contains a structural unit derived from (2) ”. The copolymer may contain other structural units. As other structural units, for example, a monomer (m2-1) and a monomer different from the monomer (m2-2) (hereinafter, "monomer (m2-3)" may be described. ), A structural unit having an ethylenically unsaturated bond, and the like. In the copolymer, each of the constituent units may contain only one type, or may contain two or more types.
　単量体（ｍ２－１）としては、例えば、以下のものが挙げられる：
　アクリル酸、メタクリル酸、クロトン酸およびｏ－、ｍ－、ｐ－ビニル安息香酸等の不飽和モノカルボン酸；
　マレイン酸、フマル酸、シトラコン酸、メサコン酸、イタコン酸、３－ビニルフタル酸、４－ビニルフタル酸、３，４，５，６－テトラヒドロフタル酸、１，２，３，６－テトラヒドロフタル酸、ジメチルテトラヒドロフタル酸および１，４－シクロヘキセンジカルボン酸等の不飽和ジカルボン酸；
　メチル－５－ノルボルネン－２，３－ジカルボン酸、５－カルボキシビシクロ［２．２．１］ヘプト－２－エン、５，６－ジカルボキシビシクロ［２．２．１］ヘプト－２－エン、５－カルボキシメチルビシクロ［２．２．１］ヘプト－２－エンおよび５－カルボキシエチルビシクロ［２．２．１］ヘプト－２－エン等のカルボキシ基を含有するビシクロ不飽和化合物；
　フマル酸およびメサコン酸を除く上記不飽和ジカルボン酸の無水物等のカルボン酸無水物；
　コハク酸モノ〔２－（メタ）アクリロイルオキシエチル〕およびフタル酸モノ〔２－（メタ）アクリロイルオキシエチル〕等の２価以上の多価カルボン酸の不飽和モノ〔（メタ）アクリロイルオキシアルキル〕エステル類；
　α－（ヒドロキシメチル）アクリル酸等の、同一分子中にヒドロキシ基およびカルボキシ基を含有する不飽和アクリレート類。 Examples of the monomer (m2-1) include the following:
Acrylic acid, methacrylic acid, crotonic acid and unsaturated monocarboxylic acids such as o-, m-, p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexendicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, Bicyclounsaturated compounds containing carboxy groups such as 5-carboxymethylbicyclo [2.2.1] hept-2-ene and 5-carboxyethylbicyclo [2.2.1] hept-2-ene;
Carboxylic anhydrides such as the above unsaturated dicarboxylic acid anhydrides excluding fumaric acid and mesaconic acid;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as mono [2- (meth) acryloyloxyethyl] and mono [2- (meth) acryloyloxyethyl] phthalates. Kind;
Unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
　単量体（ｍ２－１）としては、反応性の点や得られる樹脂のアルカリ水溶液への溶解性の点から、アクリル酸、メタクリル酸および無水マレイン酸が好ましい。 As the monomer (m2-1), acrylic acid, methacrylic acid and maleic anhydride are preferable from the viewpoint of reactivity and the solubility of the obtained resin in an alkaline aqueous solution.
　単量体（ｍ２－２）は、炭素数２～４の環状エーテル構造とエチレン性不飽和結合とを有する重合性化合物をいう。単量体（ｍ２－２）は、炭素数２～４の環状エーテル構造と（メタ）アクリロイルオキシ基とを有する単量体であることが好ましい。炭素数２～４の環状エーテル構造としては、例えば、オキシラン環、オキセタン環およびテトラヒドロフラン環が挙げられる。 The monomer (m2-2) refers to a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond. The monomer (m2-2) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group. Examples of the cyclic ether structure having 2 to 4 carbon atoms include an oxylan ring, an oxetane ring, and a tetrahydrofuran ring.
　単量体（ｍ２－２）としては、例えば、オキシラニル基とエチレン性不飽和結合とを有する単量体（以下「単量体（ｍ２－２－１）」と記載することがある）、オキセタニル基とエチレン性不飽和結合とを有する単量体（以下「単量体（ｍ２－２－２）」と記載することがある）およびテトラヒドロフリル基とエチレン性不飽和結合とを有する単量体（以下「単量体（ｍ２－２－３）」と記載することがある）等が挙げられる。 Examples of the monomer (m2-2) include a monomer having an oxylanyl group and an ethylenically unsaturated bond (hereinafter, may be referred to as “monomer (m2-2-1)”), and oxetanyl. A monomer having a group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (m2-2-2)") and a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond. (Hereinafter, it may be described as "monomer (m2-2-3)") and the like.
　単量体（ｍ２－２－１）としては、例えば、直鎖状または分岐鎖状の脂肪族不飽和炭化水素がエポキシ化された構造を有する単量体（以下「単量体（ｍ２－２－１ａ）」と記載することがある）および脂環式不飽和炭化水素がエポキシ化された構造を有する単量体（以下「（単量体ｍ２－２－１ｂ）」と記載することがある）が挙げられる。 As the monomer (m2-2-1), for example, a monomer having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter, “monomer (m2-2)”. -1a) ”) and a monomer having an alicyclic unsaturated hydrocarbon epoxidized structure (hereinafter, may be described as“ (monomer m2-2-1b) ”. ).
　単量体（ｍ２－２－１ａ）としては、グリシジル基とエチレン性不飽和結合とを有する単量体が好ましい。単量体（ｍ２－２－１ａ）としては、例えば、グリシジル（メタ）アクリレート、β－メチルグリシジル（メタ）アクリレート、β－エチルグリシジル（メタ）アクリレート、グリシジルビニルエーテル、ビニルベンジルグリシジルエーテル、α－メチルビニルベンジルグリシジルエーテル、２，３－ビス（グリシジルオキシメチル）スチレン、２，４－ビス（グリシジルオキシメチル）スチレン、２，５－ビス（グリシジルオキシメチル）スチレン、２，６－ビス（グリシジルオキシメチル）スチレン、２，３，４－トリス（グリシジルオキシメチル）スチレン、２，３，５－トリス（グリシジルオキシメチル）スチレン、２，３，６－トリス（グリシジルオキシメチル）スチレン、３，４，５－トリス（グリシジルオキシメチル）スチレンおよび２，４，６－トリス（グリシジルオキシメチル）スチレン等が挙げられる。 As the monomer (m2-2-1a), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable. Examples of the monomer (m2-2-1a) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, vinylbenzyl glycidyl ether, and α-methyl. Vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) ) Styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5 -Tris (glycidyloxymethyl) styrene and 2,4,6-tris (glycidyloxymethyl) styrene and the like can be mentioned.
　単量体（ｍ２－２－１ｂ）としては、例えば、ビニルシクロヘキセンモノオキシド、１，２－エポキシ－４－ビニルシクロヘキサン（例えば、セロキサイド（登録商標）２０００；ダイセル社製）、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート（例えば、サイクロマー（登録商標）Ａ４００；ダイセル社製）、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート（例えば、サイクロマー（登録商標）Ｍ１００；ダイセル社製）、式（ＢＩ）で表される化合物および式（ＢＩＩ）で表される化合物等が挙げられる。 Examples of the monomer (m2-2-1b) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, celloxide® 2000; manufactured by Daicel), 3,4-epoxy. Cyclohexylmethyl (meth) acrylate (eg, Cyclomer® A400; manufactured by Daicel), 3,4-epoxycyclohexylmethyl (meth) acrylate (eg, Cyclomer® M100; manufactured by Daicel), formula. Examples thereof include a compound represented by (BI) and a compound represented by the formula (BII).
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
［式（ＢＩ）および式（ＢＩＩ）中、ＲａおよびＲｂは、それぞれ独立に、水素原子、またはヒドロキシ基で置換されていてもよい炭素数１～４のアルキル基を表し、
　ＸａおよびＸｂは、それぞれ独立に、単結合、＊－Ｒｃ－、＊－Ｒｃ－Ｏ－、＊－Ｒｃ－Ｓ－または＊－Ｒｃ－ＮＨ－を表し、
　Ｒｃは、炭素数１～６のアルカンジイル基を表し、および
　＊は、Ｏとの結合位置を表す。］ [In formulas (BI) and (BII), Ra and R b each independently represent an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydrogen atom or a hydroxy group.
X a and X b are each independently a single bond, * - R c -, * - R c -O -, * - R c -S- or * -R c -NH- the stands,
R c represents an alkanediyl group having 1 to 6 carbon atoms, and * represents a bond position with O. ]
　式（ＢＩ）で表される化合物としては、例えば、式（Ｉ－１）～式（Ｉ－１５）のいずれかで表される化合物等が挙げられる。中でも、式（Ｉ－１）、式（Ｉ－３）、式（Ｉ－５）、式（Ｉ－７）、式（Ｉ－９）および式（Ｉ－１１）～式（Ｉ－１５）のいずれかで表される化合物が好ましく、式（Ｉ－１）、式（Ｉ－７）、式（Ｉ－９）および式（Ｉ－１５）のいずれかで表される化合物がより好ましい。 Examples of the compound represented by the formula (BI) include compounds represented by any of the formulas (I-1) to (I-15). Among them, formulas (I-1), formulas (I-3), formulas (I-5), formulas (I-7), formulas (I-9) and formulas (I-11) to formulas (I-15). The compound represented by any of the above is preferable, and the compound represented by any of the formula (I-1), the formula (I-7), the formula (I-9) and the formula (I-15) is more preferable.
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
　式（ＢＩＩ）で表される化合物としては、例えば、式（ＩＩ－１）～式（ＩＩ－１５）のいずれかで表される化合物等が挙げられる。中でも、式（ＩＩ－１）、式（ＩＩ－３）、式（ＩＩ－５）、式（ＩＩ－７）、式（ＩＩ－９）および式（ＩＩ－１１）～式（ＩＩ－１５）のいずれかで表される化合物が好ましく、式（ＩＩ－１）、式（ＩＩ－７）、式（ＩＩ－９）および式（ＩＩ－１５）のいずれかで表される化合物がより好ましい。 Examples of the compound represented by the formula (BII) include compounds represented by any of the formulas (II-1) to (II-15). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) and formula (II-11) to formula (II-15). The compound represented by any of the above is preferable, and the compound represented by any of the formula (II-1), the formula (II-7), the formula (II-9) and the formula (II-15) is more preferable.
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
　また、式（ＢＩ）で表される化合物および式（ＢＩＩ）で表される化合物は、それぞれ単独で用いてもよく、式（ＢＩ）で表される化合物と式（ＢＩＩ）で表される化合物とを併用してもよい。これらを併用する場合、式（ＢＩ）で表される化合物および式（ＢＩＩ）で表される化合物のモル比（式（ＢＩ）で表される化合物：式（ＢＩＩ）で表される化合物）で、好ましくは５：９５～９５：５であり、より好ましくは１０：９０～９０：１０であり、さらに好ましくは２０：８０～８０：２０である。 Further, the compound represented by the formula (BI) and the compound represented by the formula (BII) may be used independently, respectively, and the compound represented by the formula (BI) and the compound represented by the formula (BII) may be used alone. May be used in combination with. When these are used in combination, the molar ratio of the compound represented by the formula (BI) and the compound represented by the formula (BII) (the compound represented by the formula (BI): the compound represented by the formula (BII)) is used. It is preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and even more preferably 20:80 to 80:20.
　単量体（ｍ２－３）としては、例えば、以下のものが挙げられる：
　メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｓｅｃ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、シクロペンチル（メタ）アクリレート、トリシクロ［５．２．１．０２，６］デカン－８－イル（メタ）アクリレート、トリシクロ［５．２．１．０２，６］デカン－９－イル（メタ）アクリレート、トリシクロ［５．２．１．０２，６］デセン－８－イル（メタ）アクリレート、トリシクロ［５．２．１．０２，６］デセン－９－イル（メタ）アクリレート、ジシクロペンタニルオキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、アリル（メタ）アクリレート、プロパルギル（メタ）アクリレート、フェニル（メタ）アクリレート、ナフチル（メタ）アクリレートおよびベンジル（メタ）アクリレート等の（メタ）アクリレート；
　２－ヒドロキシエチル（メタ）アクリレートおよび２－ヒドロキシプロピル（メタ）アクリレート等のヒドロキシ基含有（メタ）アクリレート；
　マレイン酸ジエチル、フマル酸ジエチルおよびイタコン酸ジエチル等のジカルボン酸ジエステル；
　ビシクロ［２．２．１］ヘプト－２－エン、５－メチルビシクロ［２．２．１］ヘプト－２－エン、５－エチルビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシメチルビシクロ［２．２．１］ヘプト－２－エン、５－（２’－ヒドロキシエチル）ビシクロ［２．２．１］ヘプト－２－エン、５－メトキシビシクロ［２．２．１］ヘプト－２－エン、５－エトキシビシクロ［２．２．１］ヘプト－２－エン、５，６－ジヒドロキシビシクロ［２．２．１］ヘプト－２－エン、５，６－ジ（ヒドロキシメチル）ビシクロ［２．２．１］ヘプト－２－エン、５，６－ジ（２’－ヒドロキシエチル）ビシクロ［２．２．１］ヘプト－２－エン、５，６－ジメトキシビシクロ［２．２．１］ヘプト－２－エン、５，６－ジエトキシビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシ－５－メチルビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシ－５－エチルビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシメチル－５－メチルビシクロ［２．２．１］ヘプト－２－エン、５－ｔｅｒｔ－ブトキシカルボニルビシクロ［２．２．１］ヘプト－２－エン、５－シクロヘキシルオキシカルボニルビシクロ［２．２．１］ヘプト－２－エン、５－フェノキシカルボニルビシクロ［２．２．１］ヘプト－２－エン、５，６－ビス（ｔｅｒｔ－ブトキシカルボニル）ビシクロ［２．２．１］ヘプト－２－エンおよび５，６－ビス（シクロヘキシルオキシカルボニル）ビシクロ［２．２．１］ヘプト－２－エン等のビシクロ不飽和化合物；
　Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド、Ｎ－ベンジルマレイミド、Ｎ－スクシンイミジル－３－マレイミドベンゾエート、Ｎ－スクシンイミジル－４－マレイミドブチレート、Ｎ－スクシンイミジル－６－マレイミドカプロエート、Ｎ－スクシンイミジル－３－マレイミドプロピオネートおよびＮ－（９－アクリジニル）マレイミド等のジカルボニルイミド誘導体；
　スチレン、α－メチルスチレン、ビニルトルエンおよびｐ－メトキシスチレン等のビニル基含有芳香族化合物；
　（メタ）アクリロニトリル等のビニル基含有ニトリル；
　塩化ビニルおよび塩化ビニリデン等のハロゲン化炭化水素；
　（メタ）アクリルアミド等のビニル基含有アミド；
　酢酸ビニル等のエステル；
　１，３－ブタジエン、イソプレンおよび２，３－ジメチル－１，３－ブタジエン等のジエン。 Examples of the monomer (m2-3) include the following:
Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, Lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan-9-yl (meth) acrylate, tricyclo [5.2.1.0 2,6] decene-8-yl (meth) acrylate, tricyclo [5.2.1.0 2,6] Decene-9-yl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate , (Meta) acrylates such as naphthyl (meth) acrylates and benzyl (meth) acrylates;
Hydroxy group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-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-ene, 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-di (2'-hydroxyethyl) bicyclo [2.2. 1] Hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy -5-Methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2] .2.1] Hept-2-ene, 5-tert-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 (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5,6-bis (cyclohexyl) Bicyclounsaturated compounds such as oxycarbonyl) bicyclo [2.2.1] hept-2-ene;
N-Phenylmaleimide, N-Cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate and N- (9-acridinyl) maleimide;
Vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, vinyltoluene and p-methoxystyrene;
Vinyl group-containing nitriles such as (meth) acrylonitrile;
Halogenated hydrocarbons such as vinyl chloride and vinylidene chloride;
Vinyl group-containing amides such as (meth) acrylamide;
Esters such as vinyl acetate;
Dienes such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene.
　反応性および耐熱性の点から、単量体（ｍ２－３）としては、スチレン、ビニルトルエン、トリシクロ［５．２．１．０２，６］デカン－８－イル（メタ）アクリレート、トリシクロ［５．２．１．０２，６］デカン－９－イル（メタ）アクリレート、トリシクロ［５．２．１．０２，６］デセン－８－イル（メタ）アクリレート、トリシクロ［５．２．１．０２，６］デセン－９－イル（メタ）アクリレート、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド、Ｎ－ベンジルマレイミド、ビシクロ［２．２．１］ヘプト－２－エンおよびベンジル（メタ）アクリレートが好ましい。 From the viewpoint of reactivity and heat resistance, the monomers (m2-3) include styrene, vinyltoluene, tricyclo [5.2.1.0 2,6 ] decane-8-yl (meth) acrylate, and tricyclo [ 5.2.1.0 2,6 ] Decan-9-yl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] Desen-8-yl (meth) acrylate, tricyclo [5.2. 1.0 2,6 ] Decene-9-yl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and benzyl (meth) Acrylate is preferred.
　エチレン性不飽和結合を有する構成単位は、好ましくは（メタ）アクリロイル基を有する構成単位である。このような構成単位を有する樹脂（Ｂ２）は、単量体（ｍ２－１）に由来する構成単位および単量体（ｍ２－２）に由来する構成単位を含む重合体に、前記構成単位が有する基と反応可能な基およびエチレン性不飽和結合を有する単量体を付加させることにより得ることができる。 The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth) acryloyl group. The resin (B2) having such a structural unit is a polymer containing a structural unit derived from the monomer (m2-1) and a structural unit derived from the monomer (m2-2). It can be obtained by adding a group capable of reacting with the group having the group and a monomer having an ethylenically unsaturated bond.
　エチレン性不飽和結合を有する構成単位としては、例えば、（メタ）アクリル酸単位にグリシジル（メタ）アクリレートを付加させることによって得られる構成単位、無水マレイン酸単位に２－ヒドロキシエチル（メタ）アクリレートを付加させることによって得られる構成単位、およびグリシジル（メタ）アクリレート単位に（メタ）アクリル酸を付加させることによって得られる構成単位、ヒドロキシ基を有する構成単位にカルボン酸無水物付加させることによって得られる構成単位等が挙げられる。 As the structural unit having an ethylenically unsaturated bond, for example, a structural unit obtained by adding glycidyl (meth) acrylate to the (meth) acrylic acid unit, and 2-hydroxyethyl (meth) acrylate as the maleic anhydride unit. Constituent units obtained by addition, structural units obtained by adding (meth) acrylic acid to glycidyl (meth) acrylate units, and structural units obtained by adding carboxylic acid anhydride to structural units having a hydroxy group. Units and the like can be mentioned.
　単量体（ｍ２－１）に由来する構成単位を含む重合体は、例えば、重合開始剤の存在下、重合体の構成単位を構成する単量体を溶剤中で重合することにより製造できる。重合開始剤および溶剤等は、特に限定されず、当該分野で通常使用されているものを使用することができる。重合開始剤としては、例えば、アゾ化合物（２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（２，４－ジメチルバレロニトリル）等）や有機過酸化物（ベンゾイルペルオキシド等）が挙げられる。溶剤としては、各単量体を溶解するものであれば特に限定は無く、例えば、後述の溶剤（Ｈ）が挙げられる。なお、得られた重合体は、反応後の溶液をそのまま使用してもよいし、濃縮または希釈した溶液を使用してもよいし、再沈殿等の方法で固体（粉体）として取り出したものを使用してもよい。 A polymer containing a structural unit derived from the monomer (m2-1) can be produced, for example, by polymerizing the monomer constituting the structural unit of the polymer in a solvent in the presence of a polymerization initiator. The polymerization initiator, solvent and the like are not particularly limited, and those usually used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). Can be mentioned. The solvent is not particularly limited as long as it dissolves each monomer, and examples thereof include the solvent (H) described later. As the obtained polymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or the polymer is taken out as a solid (powder) by a method such as reprecipitation. May be used.
　単量体（ｍ２－１）に由来する構成単位を含む重合体の製造では、単量体として、エチレン性不飽和結合を有するカルボン酸無水物を使用してもよい。前記カルボン酸無水物としては、無水マレイン酸、シトラコン酸無水物、イタコン酸無水物、３－ビニルフタル酸無水物、４－ビニルフタル酸無水物、３，４，５，６－テトラヒドロフタル酸無水物、１，２，３，６－テトラヒドロフタル酸無水物、ジメチルテトラヒドロフタル酸無水物および５，６－ジカルボキシビシクロ［２．２．１］ヘプト－２－エン無水物等が挙げられる。 In the production of a polymer containing a structural unit derived from a monomer (m2-1), a carboxylic acid anhydride having an ethylenically unsaturated bond may be used as the monomer. Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic acid anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, and the like. Examples thereof include 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride.
　樹脂（Ｂ２）としては、例えば、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート／（メタ）アクリル酸共重合体、３，４－エポキシトリシクロ［５．２．１．０２，６］デシル（メタ）アクリレート／（メタ）アクリル酸共重合体、グリシジル（メタ）アクリレート／ベンジル（メタ）アクリレート／（メタ）アクリル酸共重合体、グリシジル（メタ）アクリレート／スチレン／（メタ）アクリル酸共重合体、３，４－エポキシトリシクロ［５．２．１．０２，６］デシル（メタ）アクリレート／（メタ）アクリル酸／Ｎ－シクロヘキシルマレイミド共重合体、３，４－エポキシトリシクロ［５．２．１．０２，６］デシル（メタ）アクリレート／（メタ）アクリル酸／Ｎ－シクロヘキシルマレイミド／２－ヒドロキシエチル（メタ）アクリレート共重合体、３，４－エポキシトリシクロ［５．２．１．０２，６］デシル（メタ）アクリレート／（メタ）アクリル酸／ビニルトルエン共重合体、３，４－エポキシトリシクロ［５．２．１．０２，６］デシル（メタ）アクリレート／（メタ）アクリル酸／２－エチルヘキシル（メタ）アクリレート共重合体、３，４－エポキシトリシクロ［５．２．１．０２，６］デシル（メタ）アクリレート／トリシクロ［５．２．１．０２，６］デセニル（メタ）アクリレート／（メタ）アクリル酸／Ｎ－シクロヘキシルマレイミド共重合体、３－メチル－３－（メタ）アクリルロイルオキシメチルオキセタン／（メタ）アクリル酸／スチレン共重合体、ベンジル（メタ）アクリレート／（メタ）アクリル酸共重合体、スチレン／（メタ）アクリル酸共重合体並びに特開平９－１０６０７１号公報、特開２００４－２９５１８号公報および特開２００４－３６１４５５号公報に記載の樹脂等が挙げられる。 Examples of the resin (B2) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxytricyclo [5.2.1.0 2,6 ] decyl. (Meta) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid common weight Combined, 3,4-epoxytricyclo [5.2.1.0 2,6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexyl maleimide copolymer, 3,4-epoxytricyclo [5 2.1.0 2,6 ] Decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide / 2-hydroxyethyl (meth) acrylate copolymer, 3,4-epoxytricyclo [5.2] .1.0 2,6 ] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3,4-epoxytricyclo [5.2.1.0 2,6 ] decyl (meth) acrylate / (Meta) acrylic acid / 2-ethylhexyl (meth) acrylate copolymer, 3,4-epoxytricyclo [5.2.1.0 2,6 ] decyl (meth) acrylate / tricyclo [5.2.1 .0 2,6 ] Decenyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- (meth) acrylic loyloxymethyloxetane / (meth) acrylic acid / styrene co-weight Combined, benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer and JP-A-9-106071, JP-A-2004-29518 and JP-A-2004-361455 Examples thereof include the resins described in the publication.
　２種以上の樹脂（Ｂ２）の組合せを使用する場合、前記組合せは、３，４－エポキシトリシクロ［５．２．１．０２，６］デシル（メタ）アクリレート／（メタ）アクリル酸共重合体、３，４－エポキシトリシクロ［５．２．１．０２，６］デシル（メタ）アクリレート／（メタ）アクリル酸／Ｎ－シクロヘキシルマレイミド／２－ヒドロキシエチル（メタ）アクリレート共重合体、３，４－エポキシトリシクロ［５．２．１．０２，６］デシル（メタ）アクリレート／（メタ）アクリル酸／ビニルトルエン共重合体、および３，４－エポキシトリシクロ［５．２．１．０２，６］デシル（メタ）アクリレート／（メタ）アクリル酸／２－エチルヘキシル（メタ）アクリレート共重合体からなる群から選ばれる少なくとも一つを含むことが好ましい。 When a combination of two or more resins (B2) is used, the combination is a copolymer of 3,4-epoxytricyclo [5.2.1.0 2,6 ] decyl (meth) acrylate / (meth) acrylic acid. Polymer, 3,4-epoxytricyclo [5.2.1.0 2,6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide / 2-hydroxyethyl (meth) acrylate copolymer , 3,4-Epoxytricyclo [5.2.1.0 2,6 ] decyl (meth) acrylate / (meth) acrylic acid / vinyltoluene copolymer, and 3,4-epoxytricyclo [5.2] .1.0 2,6 ] It is preferable to contain at least one selected from the group consisting of decyl (meth) acrylate / (meth) acrylic acid / 2-ethylhexyl (meth) acrylate copolymer.
　樹脂（Ｂ２）の重量平均分子量（Ｍｗ）は、好ましくは３，０００～１００，０００であり、より好ましくは５，０００～５０，０００であり、さらに好ましくは５，０００～３０，０００である。樹脂（Ｂ２）の分子量分布（Ｍｗ／Ｍｎ）（即ち、重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）の比）は、好ましくは１．１～６であり、より好ましくは１．２～４である。ここで樹脂（Ｂ２）の重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）を用いて、ポリスチレン換算にて算出される値である。 The weight average molecular weight (Mw) of the resin (B2) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. .. The molecular weight distribution (Mw / Mn) (that is, the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn)) of the resin (B2) is preferably 1.1 to 6, more preferably 1.2 to 1. It is 4. Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin (B2) are values calculated in terms of polystyrene using gel permeation chromatography (GPC).
　樹脂（Ｂ２）の酸価（固形分換算値）は、好ましくは１０～３００ｍｇＫＯＨ／ｇ、より好ましくは２０～２５０ｍｇＫＯＨ／ｇ、より一層好ましくは２０～２００ｍｇＫＯＨ／ｇ、さらに好ましくは２０～１７０ｍｇＫＯＨ／ｇであり、さらに一層好ましくは３０～１７０ｍｇＫＯＨ／ｇ、特に好ましくは５０～１５０ｍｇＫＯＨ／ｇ、特に一層好ましくは６０～１４０ｍｇＫＯＨ／ｇ、最も好ましくは６０～１３５ｍｇＫＯＨ／ｇである。樹脂（Ｂ２）の酸価は、樹脂（Ｂ２）１ｇを中和するのに必要な水酸化カリウムの量（ｍｇ）として算出される値であり、例えば水酸化カリウム水溶液を用いて滴定することにより求めることができる。 The acid value (solid content conversion value) of the resin (B2) is preferably 10 to 300 mgKOH / g, more preferably 20 to 250 mgKOH / g, even more preferably 20 to 200 mgKOH / g, still more preferably 20 to 170 mgKOH / g. It is even more preferably 30 to 170 mgKOH / g, particularly preferably 50 to 150 mgKOH / g, even more preferably 60 to 140 mgKOH / g, and most preferably 60 to 135 mgKOH / g. The acid value of the resin (B2) is a value calculated as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B2), for example, by titrating with an aqueous potassium hydroxide solution. Can be sought.
　樹脂（Ｂ２）を使用する場合、着色剤（Ａ）１００重量部に対するその含有量は、好ましくは１～１，２００重量部であり、より好ましくは５～１，０００重量部であり、さらに好ましくは１０～８００重量部である。 When the resin (B2) is used, its content with respect to 100 parts by weight of the colorant (A) is preferably 1 to 1,200 parts by weight, more preferably 5 to 1,000 parts by weight, and further preferably. Is 10 to 800 parts by weight.
　樹脂（Ｂ２）を使用する場合、固形分の総量に対するその含有量は、好ましくは１～５０重量％、より好ましくは１～４５重量％、さらに好ましくは１～４０重量％、最も好ましくは１～３０重量％である。 When the resin (B2) is used, its content with respect to the total solid content is preferably 1 to 50% by weight, more preferably 1 to 45% by weight, still more preferably 1 to 40% by weight, and most preferably 1 to 1 to 40% by weight. It is 30% by weight.
＜重合性化合物（Ｃ）＞
　重合性化合物（Ｃ）は、重合開始剤（Ｄ）から発生した活性ラジカルおよび／または酸によって重合し得る化合物である。重合性化合物（Ｃ）は、好ましくはラジカル重合性化合物である。ラジカル重合性化合物としては、例えば、重合性のエチレン性不飽和結合を有する化合物等が挙げられる。ラジカル重合性化合物は、好ましくは（メタ）アクリレート類である。 <Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by active radicals and / or acids generated from the polymerization initiator (D). The polymerizable compound (C) is preferably a radically polymerizable compound. Examples of the radically polymerizable compound include compounds having a polymerizable ethylenically unsaturated bond. The radically polymerizable compound is preferably (meth) acrylates.
　重合性化合物（Ｃ）としては、例えば、以下のものが挙げられる：
　ノニルフェニルカルビトールアクリレート、２－ヒドロキシ－３－フェノキシプロピルアクリレート、２－エチルヘキシルカルビトールアクリレート、２－ヒドロキシエチルアクリレート、Ｎ－ビニルピロリドン等の１個のエチレン性不飽和結合を有する化合物；
　１，６－ヘキサンジオールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ビスフェノールＡのビス（アクリロイロキシエチル）エーテルおよび３－メチルペンタンジオールジ（メタ）アクリレート等の２個のエチレン性不飽和結合を有する化合物；
　トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリス（２－（メタ）アクリロイルオキシエチル）イソシアヌレート等の３個のエチレン性不飽和結合を有する化合物；
　ペンタエリスリトールテトラ（メタ）アクリレート、エチレングリコール変性ペンタエリスリトールテトラ（メタ）アクリレート、プロピレングリコール変性ペンタエリスリトールテトラ（メタ）アクリレート、カプロラクトン変性ペンタエリスリトールテトラ（メタ）アクリレート等の４個のエチレン性不飽和結合を有する化合物；
　ジペンタエリスリトールペンタ（メタ）アクリレート等の５個のエチレン性不飽和結合を有する化合物；
　ジペンタエリスリトールヘキサ（メタ）アクリレート、エチレングリコール変性ジペンタエリスリトールヘキサ（メタ）アクリレート、プロピレングリコール変性ジペンタエリスリトールヘキサ（メタ）アクリレート、カプロラクトン変性ジペンタエリスリトールヘキサ（メタ）アクリレート等の６個のエチレン性不飽和結合を有する化合物；
　トリペンタエリスリトールヘプタ（メタ）アクリレート、トリペンタエリスリトールオクタ（メタ）アクリレート、テトラペンタエリスリトールノナ（メタ）アクリレート、テトラペンタエリスリトールデカ（メタ）アクリレート等の７個以上のエチレン性不飽和結合を有する化合物。 Examples of the polymerizable compound (C) include the following:
Compounds having one ethylenically unsaturated bond such as nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone;
1,6-Hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bisphenol A bis (acryloyloxyethyl) ether and Compounds with two ethylenically unsaturated bonds, such as 3-methylpentanediol di (meth) acrylate;
Compounds with three ethylenically unsaturated bonds such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2- (meth) acryloyloxyethyl) isocyanurate;
Four ethylenically unsaturated bonds such as pentaerythritol tetra (meth) acrylate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified pentaerythritol tetra (meth) acrylate. Compounds;
Compounds with 5 ethylenically unsaturated bonds such as dipentaerythritol penta (meth) acrylate;
Six ethylenic compounds such as dipentaerythritol hexa (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate. Compounds with unsaturated bonds;
A compound having seven or more ethylenically unsaturated bonds such as tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, and tetrapentaerythritol deca (meth) acrylate.
　重合性化合物（Ｃ）は、３個以上のエチレン性不飽和結合を有する重合性化合物であることが好ましく、５または６個のエチレン性不飽和結合を有する重合性化合物であることがより好ましい。具体的には、ジペンタエリスリトールペンタ（メタ）アクリレートおよびジペンタエリスリトールヘキサ（メタ）アクリレートが好ましい。重合性化合物（Ｃ）の市販品としては、例えば、ＫＡＹＡＲＡＤ（登録商標）ＤＰＨＡ（日本化薬社）、Ａ－ＴＭＭ－３ＬＭ－Ｎ（新中村化学工業社）およびＡ９５５０（新中村化学工業社）等が挙げられる。 The polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds, and more preferably a polymerizable compound having 5 or 6 ethylenically unsaturated bonds. Specifically, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable. Commercially available products of the polymerizable compound (C) include, for example, KAYARAD (registered trademark) DPHA (Nippon Kayaku Co., Ltd.), A-TMM-3LM-N (Shin-Nakamura Chemical Co., Ltd.) and A9550 (Shin-Nakamura Chemical Co., Ltd.). And so on.
　重合性化合物（Ｃ）の分子量は、好ましくは１５０以上２，９００以下、より好ましくは２５０以上１，５００以下である。なお、１，０００以上の重合性化合物（Ｃ）の分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）を用いて、ポリスチレン換算にて算出される重量平均分子量（Ｍｗ）である。 The molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 or more and 1,500 or less. The molecular weight of the polymerizable compound (C) of 1,000 or more is a weight average molecular weight (Mw) calculated in terms of polystyrene using gel permeation chromatography (GPC).
　重合性化合物（Ｃ）の含有量は、固形分の総量に対して、好ましくは７～６５重量％、より好ましくは１３～６０重量％、さらに好ましくは１７～５５重量％である。重合性化合物（Ｃ）の含有量が、前記の範囲内にあると、着色パターン形成時の残膜率およびカラーフィルタの耐薬品性が向上する傾向がある。 The content of the polymerizable compound (C) is preferably 7 to 65% by weight, more preferably 13 to 60% by weight, still more preferably 17 to 55% by weight, based on the total amount of solids. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming the coloring pattern and the chemical resistance of the color filter tend to be improved.
　また、樹脂（Ｂ）と重合性化合物（Ｃ）との重量比（樹脂（Ｂ）：重合性化合物（Ｃ））は、好ましくは２０：８０～８０：２０であり、より好ましくは３５：６５～８０：２０である。 The weight ratio of the resin (B) to the polymerizable compound (C) (resin (B): polymerizable compound (C)) is preferably 20:80 to 80:20, more preferably 35:65. ~ 80:20.
＜重合開始剤（Ｄ）＞
　重合開始剤（Ｄ）は、光または熱の作用により活性ラジカル、酸等を発生し、重合を開始し得る化合物であれば特に限定されることなく、公知の重合開始剤を用いることができる。重合開始剤（Ｄ）は、好ましくは光ラジカル重合開始剤である。重合性化合物（Ｃ）が、ラジカル重合性化合物であり、且つ重合開始剤（Ｄ）が、光ラジカル重合開始剤であること（即ち、本発明の着色硬化性樹脂組成物が、光硬化性樹脂組成物であること）がより好ましい。 <Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization by generating active radicals, acids and the like by the action of light or heat, and a known polymerization initiator can be used. The polymerization initiator (D) is preferably a photoradical polymerization initiator. The polymerizable compound (C) is a radically polymerizable compound, and the polymerization initiator (D) is a photoradical polymerization initiator (that is, the colored curable resin composition of the present invention is a photocurable resin. It is a composition) is more preferable.
　光ラジカル重合開始剤は、好ましくはＯ－アシルオキシム化合物、アルキルフェノン化合物、トリアジン化合物、アシルホスフィンオキサイド化合物およびビイミダゾール化合物からなる群から選ばれる少なくとも一つであり、より好ましくはＯ－アシルオキシム化合物である。 The photoradical polymerization initiator is preferably at least one selected from the group consisting of an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound and a biimidazole compound, and more preferably an O-acyloxime compound. Is.
　Ｏ－アシルオキシム化合物は、式（ｄ１）で表される部分構造を有する化合物である（下記式中、＊は結合位置を表す）。 The O-acyloxime compound is a compound having a partial structure represented by the formula (d1) (in the following formula, * represents a binding position).
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
　Ｏ－アシルオキシム化合物としては、例えば、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）ブタン－１－オン－２－イミン、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）オクタン－１－オン－２－イミン、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）－３－シクロペンチルプロパン－１－オン－２－イミン、Ｎ－アセトキシ－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタン－１－イミン、Ｎ－アセトキシ－１－［９－エチル－６－｛２－メチル－４－（３，３－ジメチル－２，４－ジオキサシクロペンタニルメチルオキシ）ベンゾイル｝－９Ｈ－カルバゾール－３－イル］エタン－１－イミン、Ｎ－アセトキシ－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－３－シクロペンチルプロパン－１－イミン、Ｎ－ベンゾイルオキシ－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－３－シクロペンチルプロパン－１－オン－２－イミン、Ｎ－アセチルオキシ－１－［４－（２－ヒドロキシエチルオキシ）フェニルスルファニルフェニル］プロパン－１－オン－２－イミン等が挙げられる。ＴＲ－ＰＢＧ３２７（常州強力電子新材料社製）、イルガキュア（登録商標）ＯＸＥ０１、イルガキュア（登録商標）ＯＸＥ０２、イルガキュア（登録商標）ＯＸＥ０３、イルガキュア（登録商標）ＯＸＥ０４（以上、ＢＡＳＦ社製）、Ｎ－１９１９（ＡＤＥＫＡ社製）等の市販品を用いてもよい。中でも、Ｏ－アシルオキシム化合物は、ＴＲ－ＰＢＧ３２７（常州強力電子新材料社製）、イルガキュア（登録商標）ＯＸＥ０１、イルガキュア（登録商標）ＯＸＥ０２、イルガキュア（登録商標）ＯＸＥ０３、イルガキュア（登録商標）ＯＸＥ０４（以上、ＢＡＳＦ社製）、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）ブタン－１－オン－２－イミン、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）オクタン－１－オン－２－イミンおよびＮ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）－３－シクロペンチルプロパン－１－オン－２－イミンからなる群から選ばれる少なくとも一つが好ましく、ＴＲ－ＰＢＧ３２７（常州強力電子新材料社製）、イルガキュア（登録商標）ＯＸＥ０１、イルガキュア（登録商標）ＯＸＥ０２、イルガキュア（登録商標）ＯＸＥ０３、イルガキュア（登録商標）ＯＸＥ０４（以上、ＢＡＳＦ社製）およびＮ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）オクタン－１－オン－２－イミンからなる群から選ばれる少なくとも一つがより好ましい。これらのＯ－アシルオキシム化合物を使用すると、高明度なカラーフィルタが得られる傾向にある。 Examples of the O-acyloxym compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-. 1-on-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4) -Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-Il] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropane-1 -On-2-imine, N-acetyloxy-1- [4- (2-hydroxyethyloxy) phenylsulfanylphenyl] propan-1-one-2-imine and the like can be mentioned. TR-PBG327 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), Irgacure (registered trademark) OXE01, Irgacure (registered trademark) OXE02, Irgacure (registered trademark) OXE03, Irgacure (registered trademark) OXE04 (manufactured by BASF), N- Commercially available products such as 1919 (manufactured by ADEKA) may be used. Among them, the O-acyloxime compounds are TR-PBG327 (manufactured by Joshu Strong Electronics New Materials Co., Ltd.), Irgacure (registered trademark) OXE01, Irgacure (registered trademark) OXE02, Irgacure (registered trademark) OXE03, Irgacure (registered trademark) OXE04 (registered trademark). (BASF), N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one At least one selected from the group consisting of -2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine is preferred, and TR-PBG327 (Tsunshu strong electron) New Materials Co., Ltd.), Irgacure (registered trademark) OXE01, Irgacure (registered trademark) OXE02, Irgacure (registered trademark) OXE03, Irgacure (registered trademark) OXE04 (above, manufactured by BASF) and N-benzoyloxy-1- (4) -Phenylsulfanylphenyl) More preferably at least one selected from the group consisting of octane-1-one-2-imine. The use of these O-acyloxime compounds tends to provide high brightness color filters.
　アルキルフェノン化合物は、式（ｄ２）で表される部分構造または式（ｄ３）で表される部分構造を有する化合物である（下記式中、＊は結合位置を表す）。これらの部分構造中、ベンゼン環は置換基を有していてもよい。 The alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3) (in the following formula, * represents a bond position). In these partial structures, the benzene ring may have a substituent.
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
　式（ｄ２）で表される部分構造を有する化合物としては、例えば、２－メチル－２－モルホリノ－１－（４－メチルスルファニルフェニル）プロパン－１－オン、２－ジメチルアミノ－１－（４－モルホリノフェニル）－２－ベンジルブタン－１－オン、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］ブタン－１－オン等が挙げられる。イルガキュア（登録商標）３６９、イルガキュア（登録商標）９０７、イルガキュア（登録商標）３７９（以上、ＢＡＳＦ社製）等の市販品を用いてもよい。
　式（ｄ３）で表される部分構造を有する化合物としては、例えば、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、２－ヒドロキシ－２－メチル－１－〔４－（２－ヒドロキシエトキシ）フェニル〕プロパン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチル－１－（４－イソプロペニルフェニル）プロパン－１－オンのオリゴマー、α，α－ジエトキシアセトフェノン、ベンジルジメチルケタール等が挙げられる。
　感度の点で、アルキルフェノン化合物としては、式（ｄ２）で表される部分構造を有する化合物が好ましい。 Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4). -Morphorinophenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one And so on. Commercially available products such as Irgacure (registered trademark) 369, Irgacure (registered trademark) 907, and Irgacure (registered trademark) 379 (all manufactured by BASF) may be used.
Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2). -Hydroxyethoxy) phenyl] Propane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer, α, α-diethoxy Examples thereof include acetophenone and benzyl dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).
　トリアジン化合物としては、例えば、２，４－ビス（トリクロロメチル）－６－（４－メトキシフェニル）－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－（４－メトキシナフチル）－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－ピペロニル－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－（４－メトキシスチリル）－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－〔２－（５－メチルフラン－２－イル）エテニル〕－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－〔２－（フラン－２－イル）エテニル〕－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－〔２－（４－ジエチルアミノ－２－メチルフェニル）エテニル〕－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－〔２－（３，４－ジメトキシフェニル）エテニル〕－１，３，５－トリアジン等が挙げられる。 Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-methoxy). Naftyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) )-1,3,5-Triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- [2- (fran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2) -Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, etc. Can be mentioned.
　アシルホスフィンオキサイド化合物としては、例えば、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド等が挙げられる。イルガキュア（登録商標）８１９（ＢＡＳＦ社製）等の市販品を用いてもよい。 Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.
　ビイミダゾール化合物としては、例えば、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラフェニルビイミダゾール、２，２’－ビス（２，３－ジクロロフェニル）－４，４’，５，５’－テトラフェニルビイミダゾール（例えば、特開平６－７５３７２号公報、特開平６－７５３７３号公報参照）、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラフェニルビイミダゾール、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラ（アルコキシフェニル）ビイミダゾール、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラ（ジアルコキシフェニル）ビイミダゾール、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラ（トリアルコキシフェニル）ビイミダゾール（例えば、特公昭４８－３８４０３号公報、特開昭６２－１７４２０４号公報参照）、４，４’５，５’－位のフェニル基がカルボアルコキシ基により置換されているビイミダゾール化合物（例えば、特開平７－１０９１３号公報参照）等が挙げられる。 Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl) -4. , 4', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372, JP-A-6-75373), 2,2'-bis (2-chlorophenyl) -4,4' , 5,5'-Tetraphenyl biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-) Chlorophenyl) -4,4', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxyphenyl) Biimidazole (see, for example, Japanese Patent Application Laid-Open No. 48-38403, JP-A-62-174204), a biimidazole compound in which the phenyl group at the 4,4'5,5'-position is replaced with a carboalkoxy group (for example, For example, Japanese Patent Application Laid-Open No. 7-10913) and the like can be mentioned.
　他の重合開始剤（Ｄ）としては、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾイン化合物；ベンゾフェノン、ｏ－ベンゾイル安息香酸メチル、４－フェニルベンゾフェノン、４－ベンゾイル－４’－メチルジフェニルサルファイド、３，３’，４，４’－テトラ（ｔｅｒｔ－ブチルパーオキシカルボニル）ベンゾフェノン、２，４，６－トリメチルベンゾフェノン等のベンゾフェノン化合物；９，１０－フェナンスレンキノン、２－エチルアントラキノン、カンファーキノン等のキノン化合物；１０－ブチル－２－クロロアクリドン、ベンジル、フェニルグリオキシル酸メチル、チタノセン化合物等が挙げられる。これらは、後述の重合開始助剤（Ｆ）（特にアミン類）と組み合わせて用いることが好ましい。 Examples of the other polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4 -Benzoyl-4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenance Kinone compounds such as lenquinone, 2-ethylanthraquinone, and camphorquinone; examples thereof include 10-butyl-2-chloroacrydone, benzyl, methyl phenylglycoxylate, and titanosen compounds. These are preferably used in combination with the polymerization initiator (F) (particularly amines) described later.
　酸発生剤としては、例えば、４－ヒドロキシフェニルジメチルスルホニウムｐ－トルエンスルホナート、４－ヒドロキシフェニルジメチルスルホニウムヘキサフルオロアンチモネート、４－アセトキシフェニルジメチルスルホニウムｐ－トルエンスルホナート、４－アセトキシフェニル・メチル・ベンジルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムｐ－トルエンスルホナート、トリフェニルスルホニウムヘキサフルオロアンチモネート、ジフェニルヨードニウムｐ－トルエンスルホナート、ジフェニルヨードニウムヘキサフルオロアンチモネート等のオニウム塩類、ニトロベンジルトシレート類、ベンゾイントシレート類等が挙げられる。 Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethyl. Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyltosylate, benzoin Examples include tosilates.
　重合開始剤（Ｄ）の含有量は、樹脂（Ｂ）および重合性化合物（Ｃ）の合計１００重量部に対して、好ましくは０．１～３０重量部であり、より好ましくは１～２０重量部である。重合開始剤（Ｄ）の含有量が前記の範囲内にあると、本発明の着色硬化性樹脂組成物の感度が向上し、露光時間が短縮される傾向があるため、カラーフィルタの生産性が向上する。 The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the total of the resin (B) and the polymerizable compound (C). It is a department. When the content of the polymerization initiator (D) is within the above range, the sensitivity of the color curable resin composition of the present invention tends to be improved and the exposure time tends to be shortened, so that the productivity of the color filter is increased. improves.
＜フェノール系酸化防止剤（Ｅ）＞
　本発明の着色硬化性樹脂組成物は、フェノール系酸化防止剤（Ｅ）を含むことを特徴の一つとする。フェノール系酸化防止剤（Ｅ）を使用することによって、加熱（特にポストベーク）による着色パターンまたは着色塗膜の厚さの減少を抑制することができる。また、フェノール系酸化防止剤（Ｅ）を使用することによって、着色パターンまたは着色塗膜の耐熱性を向上させ得る。 <Phenolic antioxidant (E)>
One of the features of the colored curable resin composition of the present invention is that it contains a phenolic antioxidant (E). By using the phenolic antioxidant (E), it is possible to suppress a decrease in the thickness of the colored pattern or the colored coating film due to heating (particularly post-baking). Further, by using the phenolic antioxidant (E), the heat resistance of the colored pattern or the colored coating film can be improved.
　本明細書中、「フェノール系酸化防止剤」とは、フェノール性水酸基を有する酸化防止剤を意味する。そのため、例えばフェノール性水酸基およびリン原子の両方を含む酸化防止剤は、本明細書では、リン系酸化防止剤ではなく、フェノール系酸化防止剤に分類する。また、本明細書におけるフェノール系酸化防止剤は、保護されたフェノール性水酸基を有する酸化防止剤（以下「保護されたフェノール系酸化防止剤」と記載することがある）も包含する。 In the present specification, the "phenolic antioxidant" means an antioxidant having a phenolic hydroxyl group. Therefore, for example, an antioxidant containing both a phenolic hydroxyl group and a phosphorus atom is classified as a phenolic antioxidant, not a phosphorus-based antioxidant, in the present specification. In addition, the phenolic antioxidant in the present specification also includes an antioxidant having a protected phenolic hydroxyl group (hereinafter, may be referred to as "protected phenolic antioxidant").
　フェノール系酸化防止剤としては、例えば、以下のものが挙げられる：
（１）アルキルチオメチルフェノール
　２，４－ジオクチルチオメチル－６－ｔｅｒｔ－ブチルフェノール、２，４－ジオクチルチオメチル－６－メチルフェノール、２，４－ジオクチルチオメチル－６－エチルフェノール、２，６－ジドデシルチオメチル－４－ノニルフェノール。 Examples of phenolic antioxidants include:
(1) Alkylthiomethylphenol 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6- Didodecylthiomethyl-4-nonylphenol.
（２）トコフェロール類
　α－トコフェロール、β－トコフェロール、γ－トコフェロール、δ－トコフェロール。 (2) Tocopherols α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol.
（３）Ｏ－ベンジル誘導体、Ｎ－ベンジル誘導体およびＳ－ベンジル誘導体
　３，５，３’，５’－テトラ－ｔｅｒｔ－ブチル－４，４’－ジヒドロキシジベンジルエーテル、オクタデシル－４－ヒドロキシ－３，５－ジメチルベンジルメルカプトアセテート、トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）アミン、ビス（４－ｔｅｒｔ－ブチル－３－ヒドロキシ－２，６－ジメチルベンジル）ジチオテレフタレート、ビス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）スルフィド、イソオクチル－３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルメルカプトアセテート。 (3) O-benzyl derivative, N-benzyl derivative and S-benzyl derivative 3,5,3', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3 , 5-Dimethylbenzyl mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.
（４）ヒドロキシベンジル化マロネート誘導体
　ジオクタデシル－２，２－ビス（３，５－ジ－ｔｅｒｔ－ブチル－２－ヒドロキシベンジル）マロネート、ジオクタデシル－２－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルベンジル）マロネート、ジドデシルメルカプトエチル－２，２－ビス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）マロネート、ビス［４－（１，１，３，３－テトラメチルブチル）フェニル］－２，２－ビス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）マロネート。 (4) Hydroxybenzylated malonate derivative Dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-) 5-Methylbenzyl) malonate, didodecyl mercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethyl) Butyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.
（５）芳香族ヒドロキシベンジル誘導体
　１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）ベンゼン、１，４－ビス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）－２，３，５，６－テトラメチルベンゼン、２，４，６－トリス（３，５－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）フェノール。 (5) Aromatic hydroxybenzyl derivative 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,4-bis (3,5) -Di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-tert-butyl-4-hydroxybenzyl) phenol.
（６）トリアジン誘導体
　２，４－ビス（ｎ－オクチルチオ）－６－（４－ヒドロキシ－３，５－ジ－ｔｅｒｔ－ブチルアニリノ）－１，３，５－トリアジン、２－ｎ－オクチルチオ－４，６－ビス（４－ヒドロキシ－３，５－ジ－ｔｅｒｔ－ブチルアニリノ）－１，３，５－トリアジン、２－ｎ－オクチルチオ－４，６－ビス（４－ヒドロキシ－３，５－ジ－ｔｅｒｔ－ブチルフェノキシ）－１，３，５－トリアジン、２，４，６－トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－フェノキシ）－１，３，５－トリアジン、トリス（４－ｔｅｒｔ－ブチル－３－ヒドロキシ－２，６－ジメチルベンジル）イソシアヌレート、トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）イソシアヌレート、２，４，６－トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニルエチル）－１，３，５－トリアジン、２，４，６－トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニルプロピル）－１，３，５－トリアジン、トリス（３，５－ジシクロヘキシル－４－ヒドロキシベンジル）イソシアヌレート、トリス［２－（３’，５’－ジ－ｔｅｒｔ－ブチル－４’－ヒドロキシシンナモイルオキシ）エチル］イソシアヌレート。 (6) Triazine derivative 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, 2-n-octylthio-4, 6-bis (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, 2-n-octylthio-4,6-bis (4-hydroxy-3,5-di-tert) -Butylphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-phenoxy) -1,3,5-triazine, Tris (4-tert- Butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di- tert-Butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylpropyl) -1,3,5- Triazine, tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate, tris [2- (3', 5'-di-tert-butyl-4'-hydroxycinnamoyloxy) ethyl] isocyanurate.
（７）ベンジルホスホネート誘導体
　ジメチル－３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホネート、ジエチル－３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホネート、ジオクタデシル－３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホネート、ジオクタデシル－５－ｔｅｒｔ－ブチル－４－ヒドロキシ－３－メチルベンジルホスホネート、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホン酸モノエステルのカルシウム塩。 (7) Benzylphosphonate derivative dimethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di -Calc of tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoester salt.
（８）アシルアミノフェノール誘導体
　４－ヒドロキシラウリル酸アニリド、４－ヒドロキシステアリン酸アニリド、オクチル－Ｎ－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）カルバネート。 (8) Acylaminophenol derivative 4-Hydroxylauric acid anilide, 4-hydroxystearic acid anilide, octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbanate.
（９）β－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオン酸と以下の一価または多価アルコールとのエステル
　メタノール、エタノール、オクタノール、オクタデカノール、エチレングリコール、１，３－プロパンジオール、１，４－ブタンジオール、１，６－ヘキサンジオール、１，９－ノナンジオール、ネオペンチルグリコール、ジエチレングリコール、チオエチレングリコール、スピログリコール、トリエチレングリコール、ペンタエリスリトール、トリス（ヒドロキシエチル）イソシアヌレート、Ｎ，Ｎ’－ビス（ヒドロキシエチル）オキサミド、３－チアウンデカノール、３－チアペンタデカノール、トリメチルヘキサンジオール、トリメチロールプロパン、４－ヒドロキシメチル－１－ホスファ－２，６，７－トリオキサビシクロ［２，２，２］オクタン。 (9) Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid and the following monohydric or polyhydric alcohols Methanol, ethanol, octanol, octadecanol, ethylene glycol, 1, 3-Propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) ) Isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6 , 7-Trioxabicyclo [2,2,2] octane.
（１０）β－（５－ｔｅｒｔ－ブチル－４－ヒドロキシ－３－メチルフェニル）プロピオン酸と以下の一価または多価アルコールとのエステル
　メタノール、エタノール、オクタノール、オクタデカノール、エチレングリコール、１，３－プロパンジオール、１，４－ブタンジオール、１，６－ヘキサンジオール、１，９－ノナンジオール、ネオペンチルグリコール、ジエチレングリコール、チオエチレングリコール、スピログリコール、トリエチレングリコール、ペンタエリスリトール、トリス（ヒドロキシエチル）イソシアヌレート、Ｎ，Ｎ’－ビス（ヒドロキシエチル）オキサミド、３－チアウンデカノール、３－チアペンタデカノール、トリメチルヘキサンジオール、トリメチロールプロパン、４－ヒドロキシメチル－１－ホスファ－２，６，７－トリオキサビシクロ［２，２，２］オクタン。 (10) Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid and the following monohydric or polyhydric alcohols Methanol, ethanol, octanol, octadecanol, ethylene glycol, 1, 3-Propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) ) Isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6 , 7-Trioxabicyclo [2,2,2] octane.
（１１）β－（３，５－ジシクロヘキシル－４－ヒドロキシフェニル）プロピオン酸と以下の一価または多価アルコールとのエステル
　メタノール、エタノール、オクタノール、オクタデカノール、エチレングリコール、１，３－プロパンジオール、１，４－ブタンジオール、１，６－ヘキサンジオール、１，９－ノナンジオール、ネオペンチルグリコール、ジエチレングリコール、チオエチレングリコール、スピログリコール、トリエチレングリコール、ペンタエリスリトール、トリス（ヒドロキシエチル）イソシアヌレート、Ｎ，Ｎ’－ビス（ヒドロキシエチル）オキサミド、３－チアウンデカノール、３－チアペンタデカノール、トリメチルヘキサンジオール、トリメチロールプロパン、４－ヒドロキシメチル－１－ホスファ－２，６，７－トリオキサビシクロ［２，２，２］オクタン。 (11) Ester of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid and the following monohydric or polyhydric alcohols Methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol , 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trio Kisabicyclo [2,2,2] octane.
（１２）３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル酢酸と以下の一価または多価アルコールとのエステル
　メタノール、エタノール、オクタノール、オクタデカノール、エチレングリコール、１，３－プロパンジオール、１，４－ブタンジオール、１，６－ヘキサンジオール、１，９－ノナンジオール、ネオペンチルグリコール、ジエチレングリコール、チオエチレングリコール、スピログリコール、トリエチレングリコール、ペンタエリスリトール、トリス（ヒドロキシエチル）イソシアヌレート、Ｎ，Ｎ’－ビス（ヒドロキシエチル）オキサミド、３－チアウンデカノール、３－チアペンタデカノール、トリメチルヘキサンジオール、トリメチロールプロパン、４－ヒドロキシメチル－１－ホスファ－２，６，７－トリオキサビシクロ［２，２，２］オクタン。 (12) Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid and the following monohydric or polyhydric alcohols Methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N , N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxa Bicyclo [2,2,2] octane.
（１３）β－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオン酸のアミド
　Ｎ，Ｎ’－ビス［３－（３’，５’－ジ－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオニル］ヒドラジン、Ｎ，Ｎ’－ビス［３－（３’，５’－ジ－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオニル］ヘキサメチレンジアミン、Ｎ，Ｎ’－ビス［３－（３’，５’－ジ－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオニル］トリメチレンジアミン。 (13) Amide of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid N, N'-bis [3- (3', 5'-di-tert-butyl-4'- Hydroxyphenyl) propionyl] hydrazine, N, N'-bis [3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) propionyl] hexamethylenediamine, N, N'-bis [3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) propionyl] trimethylenediamine.
　上述の例示したフェノール系酸化防止剤のフェノール性水酸基を保護基で保護したものも、本発明におけるフェノール系酸化防止剤として使用することができる。保護基としては、例えば、エーテル系保護基、アセタール系保護基、アシル系保護基、シリルエーテル系保護基が挙げられる。エーテル系保護基としては、例えば、メチル基、ベンジル基、ｐ－メトキシベンジル基、ｔｅｒｔ－ブチル基が挙げられる。アセタール系保護基としては、例えば、メトキシメチル基、２－テトラヒドロピラニル基、エトキシエチル基が挙げられる。アシル系保護基としては、アセチル基、ピバロイル基、ベンゾイル基が挙げられる。シリルエーテル系保護基としては、例えば、トリメチルシリル基、トリエチルシリル基、ｔｅｒｔ－ブチルジメチルシリル基、トリイソプロピルシリル基、ｔｅｒｔ－ブチルジフェニルシリル基が挙げられる。また、保護基として、ｔｅｒｔ－ブトキシカルボニル（Ｂｏｃ）基を使用してもよい。フェノール性水酸基の保護基としては、Ｂｏｃ基が好ましい。 The phenolic hydroxyl group of the above-exemplified phenolic antioxidant protected with a protecting group can also be used as the phenolic antioxidant in the present invention. Examples of the protecting group include ether-based protecting groups, acetal-based protecting groups, acyl-based protecting groups, and silyl ether-based protecting groups. Examples of the ether-based protecting group include a methyl group, a benzyl group, a p-methoxybenzyl group, and a tert-butyl group. Examples of the acetal-based protecting group include a methoxymethyl group, a 2-tetrahydropyranyl group, and an ethoxyethyl group. Examples of the acyl-based protecting group include an acetyl group, a pivaloyl group, and a benzoyl group. Examples of the silyl ether-based protecting group include a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a triisopropylsilyl group, and a tert-butyldiphenylsilyl group. In addition, a tert-butoxycarbonyl (Boc) group may be used as the protecting group. The Boc group is preferable as the protecting group for the phenolic hydroxyl group.
　フェノール系酸化防止剤は市販品を使用することができる。フェノール系酸化防止剤の市販品としては、例えば、スミライザー（登録商標）　ＧＰ（住友化学社製）、アデカスタブ（登録商標）　ＡＯシリーズ（ＡＤＥＫＡ社製）が挙げられる。保護されたフェノール系酸化防止剤の市販品としては、例えば、アデカアークルズ（登録商標）ＧＰＡ－５００１（ＡＤＥＫＡ社製）が挙げられる。 Commercially available products can be used as the phenolic antioxidant. Examples of commercially available phenolic antioxidants include Sumilyzer (registered trademark) GP (manufactured by Sumitomo Chemical Co., Ltd.) and ADEKA STAB (registered trademark) AO series (manufactured by ADEKA). Commercially available products of the protected phenolic antioxidant include, for example, ADEKA ARKULS® GPA-5001 (manufactured by ADEKA).
　加熱による着色パターンまたは着色塗膜の厚さ減少の抑制およびアルカリ現像後に良好な着色パターンを得る観点から、フェノール系酸化防止剤（Ｅ）の含有量は、重合性化合物（Ｃ）１００重量部に対して、好ましくは０．１～２５重量部、より好ましくは０．２～２０重量部、さらに好ましくは０．５～２０重量部、特に好ましくは３～１０重量部である。 The content of the phenolic antioxidant (E) is 100 parts by weight of the polymerizable compound (C) from the viewpoint of suppressing the decrease in the thickness of the colored pattern or the colored coating film due to heating and obtaining a good coloring pattern after alkaline development. On the other hand, it is preferably 0.1 to 25 parts by weight, more preferably 0.2 to 20 parts by weight, still more preferably 0.5 to 20 parts by weight, and particularly preferably 3 to 10 parts by weight.
＜重合開始助剤（Ｆ）＞
　本発明の着色硬化性樹脂組成物は、さらに重合開始助剤（Ｆ）を含んでいてもよい。重合開始助剤（Ｆ）は、重合開始剤によって重合が開始された重合性化合物の重合を促進するために用いられる化合物、または増感剤である。重合開始助剤（Ｆ）としては、例えば、アミン化合物、アルコキシアントラセン化合物、チオキサントン化合物およびカルボン酸化合物等が挙げられる。 <Polymerization initiator (F)>
The colored curable resin composition of the present invention may further contain a polymerization initiator (F). The polymerization initiator (F) is a compound or a sensitizer used to promote the polymerization of a polymerizable compound whose polymerization has been initiated by the polymerization initiator. Examples of the polymerization initiator (F) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds and carboxylic acid compounds.
　アミン化合物としては、例えば、トリエタノールアミン、メチルジエタノールアミン、トリイソプロパノールアミン、４－ジメチルアミノ安息香酸メチル、４－ジメチルアミノ安息香酸エチル、４－ジメチルアミノ安息香酸イソアミル、安息香酸２－ジメチルアミノエチル、４－ジメチルアミノ安息香酸２－エチルヘキシル、Ｎ，Ｎ－ジメチルパラトルイジン、４，４’－ビス（ジメチルアミノ）ベンゾフェノン（通称：ミヒラーズケトン）、４，４’－ビス（ジエチルアミノ）ベンゾフェノン、４，４’－ビス（エチルメチルアミノ）ベンゾフェノン等が挙げられる。これらの中で、４，４’－ビス（ジエチルアミノ）ベンゾフェノンが好ましい。アミン化合物としては、ＥＡＢ－Ｆ（保土谷化学工業社製）等の市販品を用いてもよい。 Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and the like. 2-Ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4' -Bis (ethylmethylamino) benzophenone and the like can be mentioned. Of these, 4,4'-bis (diethylamino) benzophenone is preferable. As the amine compound, a commercially available product such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.
　アルコキシアントラセン化合物としては、例えば、９，１０－ジメトキシアントラセン、２－エチル－９，１０－ジメトキシアントラセン、９，１０－ジエトキシアントラセン、２－エチル－９，１０－ジエトキシアントラセン、９，１０－ジブトキシアントラセン、２－エチル－９，１０－ジブトキシアントラセン等が挙げられる。 Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-. Examples thereof include dibutoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.
　チオキサントン化合物としては、例えば、２－イソプロピルチオキサントン、４－イソプロピルチオキサントン、２，４－ジエチルチオキサントン、２，４－ジクロロチオキサントン、１－クロロ－４－プロポキシチオキサントン等が挙げられる。 Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.
　カルボン酸化合物としては、例えば、フェニルスルファニル酢酸、メチルフェニルスルファニル酢酸、エチルフェニルスルファニル酢酸、メチルエチルフェニルスルファニル酢酸、ジメチルフェニルスルファニル酢酸、メトキシフェニルスルファニル酢酸、ジメトキシフェニルスルファニル酢酸、クロロフェニルスルファニル酢酸、ジクロロフェニルスルファニル酢酸、Ｎ－フェニルグリシン、フェノキシ酢酸、ナフチルチオ酢酸、Ｎ－ナフチルグリシン、ナフトキシ酢酸等が挙げられる。 Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, and dichlorophenylsulfanyl acetic acid. , N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.
　重合開始助剤（Ｆ）は、好ましくはチオキサントン化合物であり、より好ましくは２，４－ジエチルチオキサントンである。 The polymerization initiator (F) is preferably a thioxanthone compound, more preferably 2,4-diethylthioxanthone.
　重合開始助剤（Ｆ）を用いる場合、樹脂（Ｂ）および重合性化合物（Ｃ）の合計１００重量部に対するその含有量は、好ましくは０．１～３０重量部、より好ましくは１～２０重量部である。また、重合開始助剤（Ｆ）を用いる場合、重合開始剤（Ｄ）１００重量部に対するその含有量は、好ましくは５～８０重量部、より好ましくは１０～６０重量部、さらに好ましくは１５～５５重量部である。重合開始助剤（Ｆ）の量が前記範囲内にあると、高感度で着色パターンを形成することができ、カラーフィルタの生産性が向上する傾向にある。 When the polymerization initiator (F) is used, the content of the resin (B) and the polymerizable compound (C) with respect to 100 parts by weight is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight. It is a department. When the polymerization initiator (F) is used, its content with respect to 100 parts by weight of the polymerization initiator (D) is preferably 5 to 80 parts by weight, more preferably 10 to 60 parts by weight, and further preferably 15 to 15 parts by weight. It is 55 parts by weight. When the amount of the polymerization initiator (F) is within the above range, a coloring pattern can be formed with high sensitivity, and the productivity of the color filter tends to be improved.
＜チオール化合物（Ｇ）＞
　本発明の着色硬化性樹脂組成物は、さらにチオール化合物（Ｇ）を含んでいてもよい。チオール化合物（Ｇ）は、スルファニル基（－ＳＨ）を有する化合物である。 <Thiol compound (G)>
The colored curable resin composition of the present invention may further contain a thiol compound (G). The thiol compound (G) is a compound having a sulfanil group (-SH).
　１個のスルファニル基を有する化合物としては、例えば、２－スルファニルオキサゾール、２－スルファニルチアゾール、２－スルファニルベンズイミダゾール、２－スルファニルベンゾチアゾール、２－スルファニルベンゾオキサゾール、２－スルファニルニコチン酸、２－スルファニルピリジン、２－スルファニルピリジン－３－オール、２－スルファニルピリジン－Ｎ－オキサイド、４－アミノ－６－ヒドロキシ－２－スルファニルピリミジン、４－アミノ－６－ヒドロキシ－２－スルファニルピリミジン、４－アミノ－２－スルファニルピリミジン、６－アミノ－５－ニトロソ－２－チオウラシル、４，５－ジアミノ－６－ヒドロキシ－２－スルファニルピリミジン、４，６－ジアミノ－２－スルファニルピリミジン、２，４－ジアミノ－６－スルファニルピリミジン、４，６－ジヒドロキシ－２－スルファニルピリミジン、４，６－ジメチル－２－スルファニルピリミジン、４－ヒドロキシ－２－スルファニル－６－メチルピリミジン、４－ヒドロキシ－２－スルファニル－６－プロピルピリミジン、２－スルファニル－４－メチルピリミジン、２－スルファニルピリミジン、２－チオウラシル、３，４，５，６－テトラヒドロピリミジン－２－チオール、４，５－ジフェニルイミダゾール－２－チオール、２－スルファニルイミダゾール、２－スルファニル－１－メチルイミダゾール、４－アミノ－３－ヒドラジノ－５－スルファニル－１，２，４－トリアゾール、３－アミノ－５－スルファニル－１，２，４－トリアゾール、２－メチル－４Ｈ－１，２，４－トリアゾール－３－チオール、４－メチル－４Ｈ－１，２，４－トリアゾール－３－チオール、３－スルファニル１Ｈ－１，２，４－トリアゾール－３－チオール、２－アミノ－５－スルファニル－１，３，４－チアジアゾール、５－アミノ－１，３，４－チアジアゾール－２－チオール、２，５－ジスルファニル－１，３，４－チアジアゾール、（フラン－２－イル）メタンチオール、２－スルファニル－５－チアゾリドン、２－スルファニルチアゾリン、２－スルファニル－４（３Ｈ）－キナゾリノン、１－フェニル－１Ｈ－テトラゾール－５－チオール、２－キノリンチオール、２－スルファニル－５－メチルベンズイミダゾール、２－スルファニル－５－ニトロベンズイミダゾール、６－アミノ－２－スルファニルベンゾチアゾール、５－クロロ－２－スルファニルベンゾチアゾール、６－エトキシ－２－スルファニルベンゾチアゾール、６－ニトロ－２－スルファニルベンゾチアゾール、２－スルファニルナフトイミダゾール、２－スルファニルナフトオキサゾール、３－スルファニル－１，２，４－トリアゾール、４－アミノ－６－スルファニルピラゾロ［２，４－ｄ］ピリジン、２－アミノ－６－プリンチオール、６－スルファニルプリン、４－スルファニル－１Ｈ－ピラゾロ［２，４－ｄ］ピリミジン等が挙げられる。 Examples of the compound having one sulfanyl group include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanylbenzoxazole, 2-sulfanylnicotinic acid, and 2-sulfanyl. Pyridine, 2-sulfanylpyridine-3-ol, 2-sulfanylpyridine-N-oxide, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino- 2-Sulfanylpyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy-2-sulfanylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4-diamino-6 -Sulfanylpyrimidine, 4,6-dihydroxy-2-sulfanylpyrimidine, 4,6-dimethyl-2-sulfanylpyrimidine, 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl-6-propyl Pyrimidine, 2-sulfanyl-4-methylpyrimidine, 2-sulfanylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazol-2-thiol, 2-sulfanylimidazole , 2-Sulfanyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfanyl-1,2,4-triazole, 3-amino-5-sulfanyl-1,2,4-triazole, 2-methyl- 4H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 3-sulfanyl 1H-1,2,4-triazole-3-thiol, 2 -Amino-5-Sulfanyl-1,3,4-Pyrimidazole, 5-Amino-1,3,4-Pyrimidazole-2-thiol, 2,5-Disulfanyl-1,3,4-Pyrimidazole, (Fran-2) -Il) Methanthiol, 2-Sulfanyl-5-thiazolidone, 2-Sulfanylthiazolin, 2-Sulfanyl-4 (3H) -quinazolinone, 1-phenyl-1H-tetrazol-5-thiol, 2-quinolinthiol, 2-sulfanyl -5-Methylbenzimidazole, 2-Sulfanyl-5-Nitrobenzimidazole, 6-Amino-2-sulfanylbenzothiazole, 5- Chloro-2-sulfanylbenzothiazole, 6-ethoxy-2-sulfanylbenzothiazole, 6-nitro-2-sulfanylbenzothiazole, 2-sulfanylnaphthoimidazole, 2-sulfanylnaphthoxazole, 3-sulfanyl-1,2,4- Triazole, 4-amino-6-sulfanylpyrazolo [2,4-d] pyridine, 2-amino-6-purinthiol, 6-sulfanylpurine, 4-sulfanyl-1H-pyrazolo [2,4-d] pyrimidine, etc. Can be mentioned.
　２個以上のスルファニル基を有する化合物としては、例えば、ヘキサンジチオール、デカンジチオール、１，４－ビス（メチルスルファニル）ベンゼン、ブタンジオールビス（３－スルファニルプロピオネート）、ブタンジオールビス（３－スルファニルアセテート）、エチレングリコールビス（３－スルファニルアセテート）、トリメチロールプロパントリス（３－スルファニルアセテート）、ブタンジオールビス（３－スルファニルプロピオネート）、トリメチロールプロパントリス（３－スルファニルプロピオネート）（別名「トリメチロールプロパントリス（３－メルカプトプロピオネート）」）、トリメチロールプロパントリス（３－スルファニルアセテート）、ペンタエリスリトールテトラキス（３－スルファニルプロピオネート）、ペンタエリスリトールテトラキス（３－スルファニルアセテート）、トリスヒドロキシエチルトリス（３－スルファニルプロピオネート）、ペンタエリスリトールテトラキス（３－スルファニルブチレート）、１，４－ビス（３－スルファニルブチルオキシ）ブタン等が挙げられる。 Compounds having two or more sulfanyl groups include, for example, hexanedithiol, decandithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanyl propionate), butanediol bis (3-sulfanyl). Acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylpropanthris (3-sulfanyl acetate), butanediol bis (3-sulfanyl propionate), trimethylolpropanthris (3-sulfanyl propionate) (also known as "Trimethylol propanthris (3-mercaptopropionate)"), trimethyl propanthris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl acetate), tris Examples thereof include hydroxyethyltris (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate), and 1,4-bis (3-sulfanylbutyloxy) butane.
　チオール化合物（Ｇ）は、好ましくは２個以上のスルファニル基を有する化合物であり、より好ましくはトリメチロールプロパントリス（３－スルファニルプロピオネート）である。 The thiol compound (G) is preferably a compound having two or more sulfanil groups, and more preferably trimethylolpropane tris (3-sulfanil propionate).
　チオール化合物（Ｇ）を使用する場合、その含有量は、重合性化合物（Ｃ）１００重量部に対して、好ましくは０．５～２０重量部、より好ましくは１～１５重量部である。チオール化合物（Ｇ）の含有量がこの範囲内にあると、感度が高くなり、また現像性が良好になる傾向がある。 When the thiol compound (G) is used, its content is preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the polymerizable compound (C). When the content of the thiol compound (G) is within this range, the sensitivity tends to be high and the developability tends to be good.
＜溶剤（Ｈ）＞
　本発明の着色硬化性樹脂組成物は、さらに溶剤（Ｈ）を含んでいてもよい。溶剤（Ｈ）は、特に限定されず、当該分野で通常使用される溶剤を用いることができる。溶剤（Ｈ）としては、例えば、エステル溶剤（分子内に－ＣＯＯ－を含み、－Ｏ－を含まない溶剤）、エーテル溶剤（分子内に－Ｏ－を含み、－ＣＯＯ－を含まない溶剤）、エーテルエステル溶剤（分子内に－ＣＯＯ－と－Ｏ－とを含む溶剤）、ケトン溶剤（分子内に－ＣＯ－を含み、－ＣＯＯ－を含まない溶剤）、アルコール溶剤（分子内にＯＨを含み、－Ｏ－、－ＣＯ－および－ＣＯＯ－を含まない溶剤）、芳香族炭化水素溶剤、アミド溶剤、ジメチルスルホキシド等が挙げられる。なお前記「－Ｏ－」の概念には、「－ＣＯＯ－」中の「－Ｏ－」は含まれず、前記「－ＣＯ－」の概念には、「－ＣＯＯ－」中の「－ＣＯ－」は含まれない。 <Solvent (H)>
The colored curable resin composition of the present invention may further contain a solvent (H). The solvent (H) is not particularly limited, and a solvent usually used in the art can be used. Examples of the solvent (H) include an ester solvent (a solvent containing -COO- in the molecule and not containing -O-) and an ether solvent (a solvent containing -O- in the molecule and not containing -COO-). , Ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (OH in the molecule) Included, -O-, -CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like. The concept of "-O-" does not include "-O-" in "-COO-", and the concept of "-CO-" includes "-CO-" in "-COO-". Is not included.
　エステル溶剤としては、例えば、乳酸メチル、乳酸エチル、乳酸ブチル、２－ヒドロキシイソブタン酸メチル、酢酸エチル、酢酸ｎ－ブチル、酢酸イソブチル、ギ酸ペンチル、酢酸イソペンチル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、シクロヘキサノールアセテートおよびγ－ブチロラクトンなどが挙げられる。 Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and the like. Examples thereof include butyl butylate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.
　エーテル溶剤としては、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、３－メトキシ－１－ブタノール、３－メトキシ－３－メチルブタノール、テトラヒドロフラン、テトラヒドロピラン、１，４－ジオキサン、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテル、アニソール、フェネトールおよびメチルアニソールなどが挙げられる。 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, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol mono. Ethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Examples thereof include methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyletol and methyl anisole.
　エーテルエステル溶剤としては、例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル、２－メトキシ－２－メチルプロピオン酸メチル、２－エトキシ－２－メチルプロピオン酸エチル、３－メトキシブチルアセテート、３－メチル－３－メトキシブチルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテートおよびジプロピレングリコールメチルエーテルアセテートなどが挙げられる。 Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -Ethyl ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methylpropionic acid Methyl, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene Examples thereof include glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate.
　ケトン溶剤としては、例えば、４－ヒドロキシ－４－メチル－２－ペンタノン、アセトン、２－ブタノン、２－ヘプタノン、３－ヘプタノン、４－ヘプタノン、４－メチル－２－ペンタノン、ジアセトンアルコール、シクロペンタノン、シクロヘキサノンおよびイソホロンなどが挙げられる。 Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, diacetone alcohol, and cyclo. Examples include pentanone, cyclohexanone and isophorone.
　アルコール溶剤としては、例えば、メタノール、エタノール、プロパノール、ブタノール、ヘキサノール、シクロヘキサノール、エチレングリコール、プロピレングリコールおよびグリセリンなどが挙げられる。 Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.
　芳香族炭化水素溶剤としては、例えば、ベンゼン、トルエン、キシレンおよびメシチレンなどが挙げられる。 Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and mesitylene.
　アミド溶剤としては、例えば、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミドおよびＮ－メチルピロリドンなどが挙げられる。 Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.
　溶剤（Ｈ）としては、塗布性、乾燥性の点から、１ａｔｍにおける沸点が１２０℃以上１８０℃以下である有機溶剤が好ましい。溶剤（Ｈ）としては、３－メトキシ－１－ブタノール、プロピレングリコールモノメチルエーテルアセテート、乳酸エチル、プロピレングリコールモノメチルエーテル、３－エトキシプロピオン酸エチル、エチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジアセトンアルコール、４－ヒドロキシ－４－メチル－２－ペンタノンおよびＮ，Ｎ－ジメチルホルムアミドが好ましく、３－メトキシ－１－ブタノール、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、乳酸エチル、ジアセトンアルコールおよび３－エトキシプロピオン酸エチルがより好ましい。 As the solvent (H), an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm is preferable from the viewpoint of coatability and dryness. Examples of the solvent (H) include 3-methoxy-1-butanol, 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 monoethyl ether. Diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide are preferable, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diacetone alcohol. And ethyl 3-ethoxypropionate are more preferred.
　溶剤（Ｈ）を使用する場合、その含有量は、本発明の着色硬化性樹脂組成物全体に対して、好ましくは３５～９５重量％であり、より好ましくは４０～９２重量％である。言い換えると、着色硬化性樹脂組成物の固形分の総量は、好ましくは５～６５重量％、より好ましくは８～６０重量％である。溶剤（Ｈ）の含有量が前記の範囲内にあると、塗布時の平坦性が良好になり、またカラーフィルタを形成した際に色濃度が不足しないために表示特性が良好となる傾向がある。 When the solvent (H) is used, its content is preferably 35 to 95% by weight, more preferably 40 to 92% by weight, based on the entire colored curable resin composition of the present invention. In other words, the total solid content of the colored curable resin composition is preferably 5 to 65% by weight, more preferably 8 to 60% by weight. When the content of the solvent (H) is within the above range, the flatness at the time of coating is good, and the display characteristics tend to be good because the color density is not insufficient when the color filter is formed. ..
＜レベリング剤（Ｉ）＞
　本発明の着色硬化性樹脂組成物は、レベリング剤（Ｉ）を含んでいてもよい。レベリング剤（Ｉ）としては、例えば、シリコーン系界面活性剤およびフッ素系界面活性剤等が挙げられる。これらは、側鎖に重合性基を有していてもよい。 <Leveling agent (I)>
The colored curable resin composition of the present invention may contain a leveling agent (I). Examples of the leveling agent (I) include silicone-based surfactants and fluorine-based surfactants. These may have a polymerizable group in the side chain.
　シリコーン系界面活性剤としては、例えば、分子内にシロキサン結合を有する界面活性剤等が挙げられる。その市販品としては、例えば、トーレシリコーンＤＣ３ＰＡ、同ＳＨ７ＰＡ、同ＤＣ１１ＰＡ、同ＳＨ２１ＰＡ、同ＳＨ２８ＰＡ、同ＳＨ２９ＰＡ、同ＳＨ３０ＰＡ、同ＳＨ８４００（東レ・ダウコーニング社製）、ＫＰ３２１、ＫＰ３２２、ＫＰ３２３、ＫＰ３２４、ＫＰ３２６、ＫＰ３４０、ＫＰ３４１（信越化学工業社製）、ＴＳＦ４００、ＴＳＦ４０１、ＴＳＦ４１０、ＴＳＦ４３００、ＴＳＦ４４４０、ＴＳＦ４４４５、ＴＳＦ－４４４６、ＴＳＦ４４５２およびＴＳＦ４４６０（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製）等が挙げられる。 Examples of the silicone-based surfactant include a surfactant having a siloxane bond in the molecule. Examples of commercially available products include Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (manufactured by Toray Dow Corning), KP321, KP322, KP323, KP324, and KP326. , KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan GK) and the like.
　シリコーン系界面活性剤は、フッ素原子を有していてもよい。フッ素原子を有するシリコーン系界面活性剤としては、例えば、メガファック（登録商標）Ｒ０８、同ＢＬ２０、同Ｆ４７５、同Ｆ４７７および同Ｆ４４３（ＤＩＣ社製）等が挙げられる。 The silicone-based surfactant may have a fluorine atom. Examples of the silicone-based surfactant having a fluorine atom include Megafuck (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).
　フッ素系界面活性剤としては、例えば、分子内にフルオロカーボン鎖を有する界面活性剤等が挙げられる。その市販品としては、例えば、フロラード（登録商標）ＦＣ４３０、同ＦＣ４３１（住友スリーエム社製）、メガファック（登録商標）Ｆ１４２Ｄ、同Ｆ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７７、同Ｆ１８３、同Ｆ５５４、同Ｒ３０、同ＲＳ－７１８－Ｋ（ＤＩＣ社製）、エフトップ（登録商標）ＥＦ３０１、同ＥＦ３０３、同ＥＦ３５１、同ＥＦ３５２（三菱マテリアル電子化成社製）、サーフロン（登録商標）Ｓ３８１、同Ｓ３８２、同ＳＣ１０１、同ＳＣ１０５（旭硝子社製）およびＥ５８４４（（株）ダイキンファインケミカル研究所製）等が挙げられる。 Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Examples of commercially available products include Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Megafuck (registered trademark) F142D, F171, F172, F173, F177, F183, and F554. R30, RS-718-K (manufactured by DIC), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.), Surflon (registered trademark) S381, S382, Examples thereof include SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).
　レベリング剤（Ｉ）を使用する場合、その含有量は、着色硬化性樹脂組成物全体に対して、好ましくは０．００１重量％以上０．２重量％以下であり、より好ましくは０．００２重量％以上０．１重量％以下、さらに好ましくは０．０１重量％以上０．０５重量％以下である。なお、この含有量に、顔料分散液の製造に用いる分散剤の含有量は含まれない。レベリング剤（Ｉ）の含有量が前記の範囲内にあると、カラーフィルタの平坦性を良好にすることができる。 When the leveling agent (I) is used, its content is preferably 0.001% by weight or more and 0.2% by weight or less, and more preferably 0.002% by weight, based on the entire colored curable resin composition. % Or more and 0.1% by weight or less, more preferably 0.01% by weight or more and 0.05% by weight or less. It should be noted that this content does not include the content of the dispersant used in the production of the pigment dispersion liquid. When the content of the leveling agent (I) is within the above range, the flatness of the color filter can be improved.
＜その他の成分＞
　本発明の着色硬化性樹脂組成物は、必要に応じて、充填剤、他の高分子化合物、密着促進剤、光安定剤、連鎖移動剤等、当該技術分野で公知の添加剤を含んでいてもよい。 <Other ingredients>
The color curable resin composition of the present invention contains additives known in the art such as fillers, other polymer compounds, adhesion promoters, light stabilizers, chain transfer agents, etc., if necessary. May be good.
＜着色硬化性樹脂組成物の製造方法＞
　本発明の着色硬化性樹脂組成物は、例えば、着色剤（Ａ）、樹脂（Ｂ）（樹脂（Ｂ１）および必要に応じて樹脂（Ｂ２））、重合性化合物（Ｃ）、重合開始剤（Ｄ）およびフェノール系酸化防止剤（Ｅ）、並びに必要に応じて溶剤（Ｈ）、レベリング剤（Ｉ）、重合開始助剤（Ｆ）、チオール化合物（Ｇ）およびその他の成分を混合することにより調製できる。 <Manufacturing method of colored curable resin composition>
The color curable resin composition of the present invention includes, for example, a colorant (A), a resin (B) (resin (B1) and, if necessary, a resin (B2)), a polymerizable compound (C), and a polymerization initiator ( By mixing D) and a phenolic antioxidant (E) and, if necessary, a solvent (H), a leveling agent (I), a polymerization initiator (F), a thiol compound (G) and other components. Can be prepared.
　顔料（Ａ２）を用いる場合、顔料（Ａ２）を予め溶剤（Ｈ）の一部または全部と混合し、顔料（Ａ２）の平均粒子径が０．２μｍ以下程度となるまで、ビーズミルなどを用いて顔料（Ａ２）を分散させて、顔料分散液を調製することが好ましい。この際、必要に応じて分散剤、樹脂（Ｂ）（特に樹脂（Ｂ２））の一部または全部を配合してもよい。このようにして得られた顔料分散液に、残りの成分を、所定の濃度となるように混合することにより、目的の着色硬化性樹脂組成物を調製できる。 When the pigment (A2) is used, the pigment (A2) is mixed with a part or all of the solvent (H) in advance, and a bead mill or the like is used until the average particle size of the pigment (A2) is about 0.2 μm or less. It is preferable to disperse the pigment (A2) to prepare a pigment dispersion liquid. At this time, if necessary, a dispersant and a part or all of the resin (B) (particularly the resin (B2)) may be blended. The desired color-curable resin composition can be prepared by mixing the remaining components with the pigment dispersion liquid thus obtained so as to have a predetermined concentration.
　染料（Ａ１）を用いる場合、染料（Ａ１）を予め溶剤（Ｈ）の一部または全部に溶解させて、染料溶液を調製してもよい。該溶液を、孔径０．０１～１μｍ程度のフィルタでろ過することが好ましい。また、上記成分を混合して得られた着色硬化性樹脂組成物を、孔径０．０１～１０μｍ程度のフィルタでろ過することが好ましい。 When the dye (A1) is used, the dye (A1) may be dissolved in a part or all of the solvent (H) in advance to prepare a dye solution. It is preferable to filter the solution with a filter having a pore size of about 0.01 to 1 μm. Further, it is preferable to filter the colored curable resin composition obtained by mixing the above components with a filter having a pore size of about 0.01 to 10 μm.
＜カラーフィルタおよび液晶表示装置の製造方法＞
　本発明の着色硬化性樹脂組成物によりカラーフィルタを形成する方法としては、例えば、フォトリソグラフ法およびインクジェット機器を用いる方法が挙げられる。フォトリソグラフ法では、通常、着色硬化性樹脂組成物を基板上に塗布し、加熱乾燥（プリベーク）および／または減圧乾燥によって溶剤等の揮発成分を除去して組成物層を形成し、フォトマスクを介して該組成物層に光を照射（露光）し、露光後の組成物層に現像液を接触させて着色パターンを形成（現像）する工程を含む。この現像後、しばしば、着色パターンを加熱するポストベークが行われる。前記フォトリソグラフ法において露光の際にフォトマスクを用いないこと、および／または現像しないことにより、前記組成物層の硬化物である着色塗膜を形成できる。このようにして得られる着色パターンおよび着色塗膜をカラーフィルタとして用いることができる。 <Manufacturing method of color filter and liquid crystal display device>
Examples of the method for forming a color filter from the colored curable resin composition of the present invention include a photolithography method and a method using an inkjet device. In the photolithography method, a color-curable resin composition is usually applied onto a substrate, and volatile components such as a solvent are removed by heat drying (prebaking) and / or vacuum drying to form a composition layer to form a photomask. This includes a step of irradiating (exposing) the composition layer with light through the structure and bringing the developing solution into contact with the exposed composition layer to form (develop) a colored pattern. After this development, post-baking is often performed to heat the coloring pattern. By not using a photomask during exposure in the photolithography method and / or not developing it, a colored coating film which is a cured product of the composition layer can be formed. The colored pattern and colored coating film thus obtained can be used as a color filter.
　基板としては、例えば、ガラス板、樹脂板、シリコン板等が挙げられる。前記基板上に、アルミニウム、銀、銀／銅／パラジウム合金薄膜などが形成されていてもよい。さらに、前記基板上には、別のカラーフィルタ層、樹脂層、トランジスタ、回路等が形成されていてもよい。 Examples of the substrate include a glass plate, a resin plate, a silicon plate, and the like. An aluminum, silver, silver / copper / palladium alloy thin film or the like may be formed on the substrate. Further, another color filter layer, resin layer, transistor, circuit or the like may be formed on the substrate.
　作製するカラーフィルタの厚さは、特に限定されず、目的の用途等に応じて適宜調整することができ、例えば０．１～３０μｍ、好ましくは１～２０μｍ、より好ましくは１～６μｍである。 The thickness of the color filter to be produced is not particularly limited and can be appropriately adjusted according to the intended use and the like, and is, for example, 0.1 to 30 μm, preferably 1 to 20 μm, and more preferably 1 to 6 μm.
　フォトリソグラフ法による着色パターン（画素）の形成は、公知または慣用の装置や条件で行うことができる。例えば、下記のようにして着色パターンを形成することができる。 The formation of colored patterns (pixels) by the photolithography method can be performed with known or conventional devices and conditions. For example, the coloring pattern can be formed as follows.
　まず、着色硬化性樹脂組成物を基板上に塗布し、加熱乾燥（プリベーク）および／または減圧乾燥することにより溶剤等の揮発成分を除去して、平滑な組成物層を得る。塗布方法としては、例えば、スピンコート法、スリットコート法、スリット　アンド　スピンコート法等が挙げられる。 First, a colored curable resin composition is applied onto a substrate, and volatile components such as a solvent are removed by heat drying (prebaking) and / or vacuum drying to obtain a smooth composition layer. Examples of the coating method include a spin coating method, a slit coating method, a slit and spin coating method, and the like.
　次に、組成物層に、目的の着色パターンを形成するためのフォトマスクを介して光が照射される（露光）。露光面全体に均一に平行光線を照射することや、フォトマスクと組成物層が形成された基板との正確な位置合わせを行うことができるため、マスクアライナおよびステッパ等の露光装置を使用することが好ましい。 Next, the composition layer is irradiated with light through a photomask for forming a desired coloring pattern (exposure). An exposure device such as a mask aligner and a stepper should be used because it is possible to uniformly irradiate the entire exposed surface with parallel light rays and accurately align the photomask with the substrate on which the composition layer is formed. Is preferable.
　露光後の組成物層を現像液に接触させることにより、基板上に着色パターンが形成される（現像）。現像により、組成物層の未露光部が現像液に溶解して除去される。現像液としては、水酸化カリウム、炭酸水素ナトリウム、炭酸ナトリウム、水酸化テトラメチルアンモニウム等のアルカリ性化合物の水溶液が好ましい。現像方法は、パドル法、ディッピング法およびスプレー法等のいずれでもよい。さらに現像時に基板を任意の角度に傾けてもよい。現像後は、水洗することが好ましい。 A colored pattern is formed on the substrate by bringing the exposed composition layer into contact with a developing solution (development). By development, the unexposed portion of the composition layer is dissolved in a developing solution and removed. As the developing solution, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The developing method may be any of a paddle method, a dipping method, a spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.
　本発明の着色硬化性樹脂組成物から製造されるカラーフィルタは、表示装置（例えば、液晶表示装置、有機ＥＬ装置、電子ペーパー等）および固体撮像素子に用いられるカラーフィルタとして有用である。 The color filter produced from the colored curable resin composition of the present invention is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.
　以下、実施例を挙げて本発明をより具体的に説明するが、本発明はもとより下記実施例によって制限を受けるものではなく、上記・下記の趣旨に適合し得る範囲で適当に変更を加えて実施することも可能であり、それらはいずれも本発明の技術的範囲に包含される。なお、以下においては、特に断りのない限り、「部」は「重量部」を意味し、厚さ保持率以外の「％」は「重量％」を意味する。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples as well as the present invention, and appropriate modifications are made to the extent that the above and the following gist can be met. It is also possible to carry out, all of which are within the technical scope of the invention. In the following, unless otherwise specified, "part" means "part by weight", and "%" other than the thickness retention rate means "% by weight".
　以下において、化合物の構造は質量分析（ＬＣ；Ａｇｉｌｅｎｔ製１２００型、ＭＡＳＳ；Ａｇｉｌｅｎｔ製ＬＣ／ＭＳＤ型）で確認した。 In the following, the structure of the compound was confirmed by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type).
　製造例で得られた樹脂の重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）の測定は、ＧＰＣを用いて、以下の条件で行った。
　装置；Ｋ２４７９（（株）島津製作所製）
　カラム；ＳＨＩＭＡＤＺＵ　Ｓｈｉｍ－ｐａｃｋ　ＧＰＣ－８０Ｍ
　カラム温度；４０℃
　溶媒；ＴＨＦ（テトラヒドロフラン）
　流速；１．０ｍＬ／ｍｉｎ
　検出器；ＲＩ
　校正用標準物質；ＴＳＫ　ＳＴＡＮＤＡＲＤ　ＰＯＬＹＳＴＹＲＥＮＥ　Ｆ－４０、Ｆ－４、Ｆ－２２８、Ａ－２５００、Ａ－５００（東ソー社製）
　上記で得られたポリスチレン換算の重量平均分子量および数平均分子量の比（Ｍｗ／Ｍｎ）を分子量分布とした。 The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the production example were measured by using GPC under the following conditions.
Equipment: K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shima-pack GPC-80M
Column temperature; 40 ° C
Solvent; THF (tetrahydrofuran)
Flow velocity; 1.0 mL / min
Detector; RI
Calibration standard material; TSK STANDARD POLYSTYRENE F-40, F-4, F-228, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight and the number average molecular weight obtained above was used as the molecular weight distribution.
＜製造例１：樹脂（Ｂ１－１）の製造＞
　撹拌装置、滴下ロート、コンデンサー、温度計およびガス導入管を備えたフラスコに、３－メトキシブタノール７５０．０ｇを入れ、窒素置換しながら撹拌し、８０℃に昇温した。
　次に、メタクリル酸２５．６ｇ（０．３０モル）、３－メタクリロイルオキシプロピルトリメトキシシラン１４６．４ｇ（０．５０モル）およびメチルメタクリレート４９．２ｇ（０．４９モル）からなるモノマー混合物に、２，２’－アゾビス（２，４－ジメチルバレロニトリル）（重合開始剤）２８．８ｇを添加したものを、滴下ロートから前記フラスコ中に滴下した。
　滴下終了後、８０℃にて混合物を５時間撹拌して共重合反応を行い、樹脂（Ｂ１－１）（重量平均分子量（Ｍｗ）：５，５００、酸価：８２ｍｇＫＯＨ／ｇ、シリル基当量：５００）を得た。 <Manufacturing Example 1: Production of Resin (B1-1)>
750.0 g of 3-methoxybutanol was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introduction tube, and the mixture was stirred while being replaced with nitrogen, and the temperature was raised to 80 ° C.
Next, a monomer mixture consisting of 25.6 g (0.30 mol) of methacrylate, 146.4 g (0.50 mol) of 3-methacryloyloxypropyltrimethoxysilane and 49.2 g (0.49 mol) of methyl methacrylate was added to the monomer mixture. 28.8 g of 2,2'-azobis (2,4-dimethylvaleronitrile) (polymerization initiator) was added dropwise to the flask from the dropping funnel.
After completion of the dropping, the mixture was stirred at 80 ° C. for 5 hours to carry out a copolymerization reaction, and the resin (B1-1) (weight average molecular weight (Mw): 5,500, acid value: 82 mgKOH / g, silyl group equivalent: 500) was obtained.
＜製造例２：樹脂（Ｂ１－２）の製造＞
　撹拌装置、滴下ロート、コンデンサー、温度計およびガス導入管を備えたフラスコに、プロピレングリコールモノメチルエーテル７５０．０ｇを入れ、窒素置換しながら撹拌し、８０℃に昇温した。
　次に、メタクリル酸３９．２ｇ（０．４６モル）、３－メタクリロイルオキシプロピルトリエトキシシラン１３２．０ｇ（０．４６モル）およびジシクロペンタニルメタクリレート５０．１ｇ（０．２３モル）からなるモノマー混合物に、２，２’－アゾビス（２，４－ジメチルバレロニトリル）（重合開始剤）２８．８ｇを添加したものを、滴下ロートから前記フラスコ中に滴下した。
　滴下終了後、８０℃にて混合物を５時間撹拌して共重合反応を行い、樹脂（Ｂ１－２）（重量平均分子量（Ｍｗ）：４，０００、酸価：１３５ｍｇＫＯＨ／ｇ、シリル基当量：５５０）を得た。 <Manufacturing example 2: Production of resin (B1-2)>
750.0 g of propylene glycol monomethyl ether was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introduction tube, and the mixture was stirred while replacing nitrogen, and the temperature was raised to 80 ° C.
Next, a monomer consisting of 39.2 g (0.46 mol) of methacrylic acid, 132.0 g (0.46 mol) of 3-methacryloyloxypropyltriethoxysilane and 50.1 g (0.23 mol) of dicyclopentanyl methacrylate. 28.8 g of 2,2'-azobis (2,4-dimethylvaleronitrile) (polymerization initiator) was added to the mixture, and the mixture was added dropwise from the dropping funnel into the flask.
After completion of the dropping, the mixture was stirred at 80 ° C. for 5 hours to carry out a copolymerization reaction, and the resin (B1-2) (weight average molecular weight (Mw): 4,000, acid value: 135 mgKOH / g, silyl group equivalent: 550) was obtained.
＜製造例３：樹脂（Ｂ２－１）の製造＞
　還流冷却器、滴下ロートおよび撹拌機を備えたフラスコ内に窒素雰囲気に置換し、プロピレングリコールモノメチルエーテルアセテート２８０部を入れ、撹拌しながら８０℃まで加熱した。次いで、アクリル酸３８部、３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－８－イルアクリレートおよび３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－９－イルアクリレートの混合物（含有比はモル比で１：１）２８９部、プロピレングリコールモノメチルエーテルアセテート１２５部の混合溶液を５時間かけて滴下した。一方、２，２－アゾビス（２，４－ジメチルバレロニトリル）３３部をプロピレングリコールモノメチルエーテルアセテート２３５部に溶解させた溶液を６時間かけて滴下した。滴下終了後、混合物を８０℃で４時間保持した後、室温まで冷却して、固形分３５．１％、Ｂ型粘度計（２３℃）で測定した粘度１２５ｍＰａｓの共重合体（樹脂（Ｂ２－１））溶液を得た。得られた共重合体の重量平均分子量（Ｍｗ）は９．２×１０３、分子量分布（Ｍｗ／Ｍｎ）２．０８、酸価（固形分換算値）は７７ｍｇＫＯＨ／ｇであった。樹脂（Ｂ２－１）は以下の構成単位を有する（下記式中、＊は結合位置を示す。）。 <Manufacturing Example 3: Production of Resin (B2-1)>
The flask was replaced with a nitrogen atmosphere in a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and 280 parts of propylene glycol monomethyl ether acetate was placed therein and heated to 80 ° C. with stirring. Then 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 2,6 ] . 6 ] A mixed solution of 289 parts of a mixture of decane-9-ylacrylate (content ratio: 1: 1 in molar ratio) and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a solution prepared by dissolving 33 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropping, the mixture was held at 80 ° C. for 4 hours, cooled to room temperature, and a copolymer having a solid content of 35.1% and a viscosity of 125 mPas measured with a B-type viscometer (23 ° C.) (resin (B2-)). 1)) A solution was obtained. The weight average molecular weight of the resultant copolymer (Mw) of 9.2 × 10 3, the molecular weight distribution (Mw / Mn) 2.08, acid value (in terms of solid content) was 77 mgKOH / g. The resin (B2-1) has the following structural units (in the following formula, * indicates a bonding position).
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
＜製造例４：赤色顔料の分散液の製造＞
　後述のようにして合成した赤色顔料５０．６部、分散剤（ＢＹＫ社製　ＢＹＫＬＰＮ－６９１９；プロピレングリコールモノメチルエーテルアセテート６０％溶液）１０．１部、樹脂（Ｂ２－１）２０．３部（固形分換算）、プロピレングリコールモノメチルエーテル６４．５部およびプロピレングリコールモノメチルエーテルアセテート２１６．０部を混合し、０．４μｍのジルコニアビーズ６００部を加え、ペイントコンディショナー（ＬＡＵ社製）を使用して、得られた混合物を１時間振盪した。その後、ジルコニアビーズをろ過により除去して赤色顔料の分散液を得た。 <Production Example 4: Production of dispersion of red pigment>
50.6 parts of red pigment synthesized as described below, 10.1 parts of dispersant (BYKLPN-6919 manufactured by BYK; 60% solution of propylene glycol monomethyl ether acetate), 20.3 parts of resin (B2-1) (solid) (Minute conversion), 64.5 parts of propylene glycol monomethyl ether and 216.0 parts of propylene glycol monomethyl ether acetate are mixed, 600 parts of 0.4 μm zirconia beads are added, and a paint conditioner (manufactured by LAU) is used. The mixture was shaken for 1 hour. Then, the zirconia beads were removed by filtration to obtain a dispersion liquid of a red pigment.
　赤色顔料の分散液の製造に使用した赤色顔料は、次のように合成した。
　１７４ｇのｔｅｒｔ－アミルアルコールと金属ナトリウム２２．２ｇとを窒素雰囲気下１３０℃で反応させてナトリウムｔｅｒｔ－アミルアルコラートを合成した。これを６０℃に加熱し、４－ブロモベンゾニトリル９１．０ｇ、コハク酸ジ－ｔｅｒｔ－アミルエステル７１．０５ｇ、およびｔｅｒｔ－アミルアルコール１０８．９ｇを加え、得られた懸濁液の温度を８５℃以下になるように、懸濁液を２時間攪拌した。この懸濁液を、８５℃でそのまま１８時間以上攪拌した後、－１０℃に冷却したメタノール２００ｇと水１０００ｇと硫酸４９．２１ｇとの混合液に加えた。懸濁液の添加が終了した後、得られた混合物を、０℃に保ちながら５時間攪拌して反応を完了させた後、固形物を濾過により回収した。回収した固形物は、メタノールおよび水で交互に洗浄した。この洗浄は、洗浄に使用したメタノールおよび水の着色がなくなり、かつ塩の析出がなくなるまで繰り返し行った。洗浄後の固形物を８０℃の真空乾燥機で１８時間乾燥し、赤色顔料を得た。 The red pigment used in the production of the dispersion liquid of the red pigment was synthesized as follows.
Sodium tert-amyl alcoholate was synthesized by reacting 174 g of tert-amyl alcohol with 22.2 g of metallic sodium at 130 ° C. under a nitrogen atmosphere. This was heated to 60 ° C., 91.0 g of 4-bromobenzonitrile, 71.05 g of di-tert-amyl ester succinate, and 108.9 g of tert-amyl alcohol were added, and the temperature of the obtained suspension was 85. The suspension was stirred for 2 hours so that the temperature was below ° C. This suspension was stirred as it was at 85 ° C. for 18 hours or more, and then added to a mixed solution of 200 g of methanol cooled to −10 ° C., 1000 g of water, and 49.21 g of sulfuric acid. After the addition of the suspension was completed, the obtained mixture was stirred for 5 hours while maintaining the temperature at 0 ° C. to complete the reaction, and then the solid was collected by filtration. The recovered solids were washed alternately with methanol and water. This washing was repeated until the methanol and water used for the washing were no longer colored and no salt was precipitated. The washed solid was dried in a vacuum dryer at 80 ° C. for 18 hours to obtain a red pigment.
＜製造例５：青色顔料の分散液の製造＞
　Ｃ．Ｉ．ピグメント・ブルー１５：６　１９．２部、分散剤（ＢＹＫ社製　ＢＹＫＬＰＮ－６９１９；プロピレングリコールモノメチルエーテルアセテート６０％溶液）６．７部、樹脂（Ｂ２－１）７．７部（固形分換算）、乳酸エチル１４．６部およびプロピレングリコールモノメチルエーテルアセテート１４３．８部を混合し、０．４μｍのジルコニアビーズ６００部を加え、ペイントコンディショナー（ＬＡＵ社製）を使用して、得られた混合物を１時間振盪した。その後、ジルコニアビーズをろ過により除去して青色顔料の分散液を得た。 <Production Example 5: Production of dispersion of blue pigment>
C. I. Pigment Blue 15: 6 19.2 parts, dispersant (BYKLPN-6919 manufactured by BYK; 60% solution of propylene glycol monomethyl ether acetate) 6.7 parts, resin (B2-1) 7.7 parts (solid content conversion) , 14.6 parts of ethyl lactate and 143.8 parts of propylene glycol monomethyl ether acetate are mixed, 600 parts of 0.4 μm zirconia beads are added, and 1 part of the obtained mixture is added using a paint conditioner (manufactured by LAU). Shake for hours. Then, the zirconia beads were removed by filtration to obtain a dispersion liquid of a blue pigment.
＜製造例６：化合物（Ａ３－１－１）の製造＞
　特開２０１８－１２７５９６号公報の実施例７に記載の方法により、下記式（Ａ３－１－１）で表される化合物を製造した。 <Production Example 6: Production of compound (A3-1-1)>
A compound represented by the following formula (A3-1-1) was produced by the method described in Example 7 of JP-A-2018-127596.
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
＜製造例７：化合物（Ａ３－２－１）の製造＞
　特開２０１５－３８２０１号公報の合成例１９に記載の方法により、下記式（Ａ３－２－１）で表される化合物を製造した。 <Production Example 7: Production of compound (A3-2-1)>
A compound represented by the following formula (A3-2-1) was produced by the method described in Synthesis Example 19 of JP2015-38201.
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
＜製造例８：化合物（Ａ３－１－１）の分散液の製造＞
　化合物（Ａ３－１－１）７部、分散剤（ビックケミー社製　ＤＩＳＰＥＲＢＹＫ（登録商標）－２０５０；プロピレングリコールモノメチルエーテルアセテート５２％溶液）３部、樹脂（Ｂ２－１）（固形分換算）３部、プロピレングリコールモノメチルエーテルアセテート８１部、ジアセトンアルコール６部および０．２ｍｍのジルコニアビーズ３００部を混合し、ペイントコンディショナー（ＬＡＵ社製）を使用して、得られた混合物を３時間振盪した。その後、ジルコニアビーズをろ過により除去して、化合物（Ａ３－１－１）の分散液を製造した。なお、化合物（Ａ３－１－１）はジアセトンアルコールに溶解する染料であるが、耐熱性および耐光性に関する化合物（Ａ３－１－１）の信頼性を向上させるため、プロピレングリコールモノメチルエーテルアセテートを使用して、化合物（Ａ３－１－１）の分散液を製造し、これを使用した。 <Production Example 8: Production of dispersion of compound (A3-1-1)>
7 parts of compound (A3-1-1), 3 parts of dispersant (DISPERBYK (registered trademark) -2050 manufactured by Big Chemie; 52% solution of propylene glycol monomethyl ether acetate), 3 parts of resin (B2-1) (solid content conversion) , 81 parts of propylene glycol monomethyl ether acetate, 6 parts of diacetone alcohol and 300 parts of 0.2 mm zirconia beads were mixed, and the obtained mixture was shaken for 3 hours using a paint conditioner (manufactured by LAU). Then, the zirconia beads were removed by filtration to produce a dispersion of the compound (A3-1-1). The compound (A3-1-1) is a dye that dissolves in diacetone alcohol. However, in order to improve the reliability of the compound (A3-1-1) regarding heat resistance and light resistance, propylene glycol monomethyl ether acetate is used. It was used to produce a dispersion of compound (A3-1-1), which was used.
＜製造例９：化合物（Ａ３－２－１）の分散液の製造＞
　化合物（Ａ３－２－１）１４部、分散剤（ＢＹＫ社製　ＢＹＫＬＰＮ－６９１９；プロピレングリコールモノメチルエーテルアセテート６０％溶液）２部、樹脂（Ｂ２－１）（固形分換算）６部、プロピレングリコールモノメチルエーテルアセテート７４部、ジアセトンアルコール４部および０．２ｍｍのジルコニアビーズ３００部を混合し、ペイントコンディショナー（ＬＡＵ社製）を使用して、得られた混合物を３時間振盪した。その後、ジルコニアビーズをろ過により除去して、化合物（Ａ３－２－１）の分散液を製造した。なお、化合物（Ａ３－２－１）はジアセトンアルコールに溶解する染料であるが、耐熱性および耐光性に関する化合物（Ａ３－２－１）の信頼性を向上させるため、プロピレングリコールモノメチルエーテルアセテートを使用して、化合物（Ａ３－２－１）の分散液を製造し、これを使用した。 <Production Example 9: Production of dispersion of compound (A3-2-1)>
Compound (A3-2-1) 14 parts, dispersant (BYKLPN-6919 manufactured by BYK; propylene glycol monomethyl ether acetate 60% solution) 2 parts, resin (B2-1) (solid content equivalent) 6 parts, propylene glycol monomethyl 74 parts of ether acetate, 4 parts of diacetone alcohol and 300 parts of 0.2 mm zirconia beads were mixed, and the obtained mixture was shaken for 3 hours using a paint conditioner (manufactured by LAU). Then, the zirconia beads were removed by filtration to produce a dispersion of the compound (A3-2-1). The compound (A3-2-1) is a dye that dissolves in diacetone alcohol. However, in order to improve the reliability of the compound (A3-2-1) regarding heat resistance and light resistance, propylene glycol monomethyl ether acetate is used. It was used to produce a dispersion of compound (A3-2-1), which was used.
実施例１～１６および比較例１～５
（１）着色硬化性樹脂組成物の製造
　下記表１～３に示す組成となるように各成分を混合して、着色硬化性樹脂組成物を得た。 Examples 1 to 16 and Comparative Examples 1 to 5
(1) Production of Color Curable Resin Composition Each component was mixed so as to have the compositions shown in Tables 1 to 3 below to obtain a color curable resin composition.
　着色硬化性樹脂組成物の製造に使用した各成分は以下の通りである。
＜染料（Ａ１）＞
　（Ａ１－１）：特開２０１６－２７０７５の実施例１に記載の方法によって得られた下記式（Ａ１－１）で表される染料
　（Ａ１－２）：特開２０１７－２２６８１４の実施例２に記載の方法によって得られた下記式（Ａ１－２）で表される染料
　（Ａ１－３）：特開２０１６－１７６０７５の合成例２に記載の方法によって得られた下記式（Ａ１－３）で表される染料 The components used in the production of the color curable resin composition are as follows.
<Dye (A1)>
(A1-1): Dye represented by the following formula (A1-1) obtained by the method described in Example 1 of JP-A-2016-27075 (A1-2): Example 2 of JP-A-2017-226814. Dye represented by the following formula (A1-2) obtained by the method described in (A1-3): The following formula (A1-3) obtained by the method described in Synthesis Example 2 of JP-A-2016-176075. Dye represented by
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
＜顔料（Ａ２）の分散液＞
　赤色顔料の分散液：製造例４で得られた分散液
　青色顔料の分散液：製造例５で得られた分散液 <Dispersion of pigment (A2)>
Dispersion liquid of red pigment: Dispersion liquid obtained in Production Example 4 Dispersion liquid of blue pigment: Dispersion liquid obtained in Production Example 5
＜化合物（Ａ３）の分散液＞
　化合物（Ａ３－１－１）の分散液：製造例８で得られた分散液
　化合物（Ａ３－２－１）の分散液：製造例９で得られた分散液 <Dispersion of compound (A3)>
Dispersion of compound (A3-1-1): dispersion obtained in Production Example 8 Dispersion of compound (A3-2-1): dispersion obtained in Production Example 9
＜樹脂（Ｂ）＞
　（Ｂ１－１）：製造例１で得られた樹脂（Ｂ１－１）
　（Ｂ１－２）：製造例２で得られた樹脂（Ｂ１－２）
　（Ｂ２－１）：製造例３で得られた樹脂（Ｂ２－１）（顔料（Ａ２）の分散液の製造、化合物（Ａ３）の分散液の製造、および比較例４で使用） <Resin (B)>
(B1-1): Resin (B1-1) obtained in Production Example 1.
(B1-2): Resin obtained in Production Example 2 (B1-2)
(B2-1): Resin (B2-1) obtained in Production Example 3 (used in production of a dispersion liquid of pigment (A2), production of a dispersion liquid of compound (A3), and Comparative Example 4).
＜重合性化合物（Ｃ）＞
　（Ｃ－１）：ジペンタエリスリトールヘキサアクリレート（日本化薬社製「ＫＡＹＡＲＡＤ（登録商標）　ＤＰＨＡ」） <Polymerizable compound (C)>
(C-1): Dipentaerythritol hexaacrylate ("KAYARAD (registered trademark) DPHA" manufactured by Nippon Kayaku Co., Ltd.)
＜重合開始剤（Ｄ）＞
　（Ｄ－１）：下記式（Ｄ－１）で表される化合物（常州強力電子新材料社製「ＴＲ－ＰＢＧ３２７」）
　（Ｄ－２）：ＢＡＳＦ社製「イルガキュア（登録商標）９０７」 <Polymerization initiator (D)>
(D-1): Compound represented by the following formula (D-1) (“TR-PBG327” manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.)
(D-2): BASF's "Irgacure (registered trademark) 907"
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
＜フェノール系酸化防止剤（Ｅ）＞
　（Ｅ－１）：６－［３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロポキシ］－２，４，８，１０－テトラ－ｔｅｒｔ－ブチルジベンズ［ｄ，ｆ］［１．３．２］ジオキサホスフェピン（住友化学社製「スミライザー（登録商標）　ＧＰ」）
　（Ｅ－２）：ＡＤＥＫＡ社製「アデカアークルズ（登録商標）ＧＰＡ－５００１」
　（Ｅ－３）：ＡＤＥＫＡ社製「アデカスタブ（登録商標）ＡＯ－６０」 <Phenolic antioxidant (E)>
(E-1): 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1 .3.2] Dioxaphosfepine (Sumitomo Chemical Co., Ltd. "Sumilyzer (registered trademark) GP")
(E-2): "ADEKA Arkuru's (registered trademark) GPA-5001" manufactured by ADEKA Corporation.
(E-3): "ADEKA STAB (registered trademark) AO-60" manufactured by ADEKA Corporation
＜リン系酸化防止剤＞
　ＴＰＰ：トリフェニルホスファイト（ＡＤＥＫＡ社製「アデカスタブ（登録商標）ＴＰＰ」） <Phosphorus antioxidant>
TPP: Triphenyl phosphate ("ADEKA STAB (registered trademark) TPP" manufactured by ADEKA)
＜重合開始助剤（Ｆ）＞
　（Ｆ－１）：２，４－ジエチルチオキサントン（日本化薬社製「ＫＡＹＡＣＵＲＥ（登録商標）　ＤＥＴＸ－Ｓ」） <Polymerization initiator (F)>
(F-1): 2,4-Diethylthioxanthone (“KAYACURE (registered trademark) DETX-S” manufactured by Nippon Kayaku Co., Ltd.)
＜チオール化合物（Ｇ）＞
（Ｇ－１）：トリメチロールプロパントリス（３－メルカプトプロピオネート）（ＳＣ有機化学社製） <Thiol compound (G)>
(G-1): Trimethylolpropanetris (3-mercaptopropionate) (manufactured by SC Organic Chemistry Co., Ltd.)
＜溶剤（Ｈ）＞
　（Ｈ－１）：３－メトキシ－１－ブタノール（東京化成工業社製、沸点１５８℃）
　（Ｈ－２）：ジアセトンアルコール（東京化成工業社製、沸点１６８℃）
　（Ｈ－３）：プロピレングリコールモノメチルエーテルアセテート（ＫＨネオケム社製、１４６℃）
　（Ｈ－４）：プロピレングリコールモノメチルエーテル（ＫＨネオケム社製、沸点１２１℃） <Solvent (H)>
(H-1): 3-Methoxy-1-butanol (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 158 ° C.)
(H-2): Diacetone alcohol (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 168 ° C)
(H-3): Propylene glycol monomethyl ether acetate (manufactured by KH Neochem, 146 ° C)
(H-4): Propylene glycol monomethyl ether (manufactured by KH Neochem, boiling point 121 ° C.)
＜レベリング剤（Ｉ）＞
　（Ｉ－１）：シリコーン系界面活性剤（東レ・ダウコーニング社製「トーレシリコーンＳＨ８４００」） <Leveling agent (I)>
(I-1): Silicone-based surfactant ("Torre Silicone SH8400" manufactured by Toray Dow Corning)
（２）カラーフィルタ（着色塗膜）の形成
　２インチ角のガラス基板（イーグル２０００；コーニング社製）上に、着色硬化性樹脂組成物をスピンコート法で塗布した後、１００℃で３分間プリベークして、組成物層を形成した。冷却後、露光機（ＴＭＥ－１５０ＲＳＫ；トプコン社製）を用いて、大気雰囲気下、６０ｍＪ／ｃｍ２の露光量（３６５ｎｍ基準）で組成物層に光照射した。光照射後、オーブン中、２３０℃で２０分間ポストベークを行うことにより、着色塗膜を得た。放冷後、得られた着色塗膜の厚さを、膜厚測定装置（ＤＥＫＴＡＫ３；日本真空技術社製））を用いて測定したところ、３．０μｍであった。 (2) Formation of color filter (colored coating film) A colored curable resin composition is applied on a 2-inch square glass substrate (Eagle 2000; manufactured by Corning Inc.) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes. To form a composition layer. After cooling, the composition layer was irradiated with light at an exposure amount of 60 mJ / cm 2 (based on 365 nm) in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon). After light irradiation, a colored coating film was obtained by post-baking at 230 ° C. for 20 minutes in an oven. After allowing to cool, the thickness of the obtained colored coating film was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.) and found to be 3.0 μm.
（３）厚さ保持率の評価
　形成された着色塗膜のポストベーク前後の厚さを、膜厚測定装置（ＤＥＫＴＡＫ３；日本真空技術社製）を用いて測定し、下記式：
　厚さ保持率（％）＝（ポストベーク後の厚さ／ポストベーク前の厚さ）×１００
に従って厚さ保持率を算出した。結果を表１～３に示す。 (3) Evaluation of thickness retention rate The thickness of the formed colored coating film before and after post-baking was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), and the following formula:
Thickness retention rate (%) = (thickness after post-baking / thickness before post-baking) x 100
The thickness retention rate was calculated according to. The results are shown in Tables 1 to 3.
Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000047
  
Figure JPOXMLDOC01-appb-T000047
  
Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000048
　表１～３に示す結果から明らかなように、フェノール系酸化防止剤および樹脂（Ｂ１）（即ち、樹脂（Ｂ１－１）または樹脂（Ｂ１－２））を使用した実施例１～１６の着色硬化性樹脂組成物は、酸化防止剤を使用しない比較例１、３および５、またはフェノール系酸化防止剤の代わりにリン系酸化防止剤を使用した比較例２、樹脂（Ｂ１）を使用しない比較例４の着色硬化性樹脂組成物に比べて、ポストベークによる着色塗膜の厚さ減少を抑制することができる。 As is clear from the results shown in Tables 1 to 3, coloring of Examples 1 to 16 using a phenolic antioxidant and a resin (B1) (that is, a resin (B1-1) or a resin (B1-2)). The curable resin composition is Comparative Examples 1, 3 and 5 in which no antioxidant is used, or Comparative Example 2 in which a phosphorus-based antioxidant is used instead of the phenol-based antioxidant, and a comparison in which the resin (B1) is not used. Compared with the colored curable resin composition of Example 4, it is possible to suppress a decrease in the thickness of the colored coating film due to post-baking.
　本発明の着色硬化性樹脂組成物を用いれば、加熱（特にポストベーク）による着色パターンまたは着色塗膜の厚さの減少を抑制することができる。本発明の着色硬化性樹脂組成物から製造されるカラーフィルタは、表示装置（例えば、液晶表示装置、有機ＥＬ装置、電子ペーパー等）および固体撮像素子に用いられるカラーフィルタとして有用である。 By using the colored curable resin composition of the present invention, it is possible to suppress a decrease in the thickness of the colored pattern or the colored coating film due to heating (particularly post-baking). The color filter produced from the colored curable resin composition of the present invention is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

Claims (9)

  1. 　着色剤（Ａ）、樹脂（Ｂ）、重合性化合物（Ｃ）および重合開始剤（Ｄ）を含む着色硬化性樹脂組成物であって、
    　着色硬化性樹脂組成物が、さらにフェノール系酸化防止剤（Ｅ）を含み、
    　樹脂（Ｂ）が、式（１ｂ）：
    Figure JPOXMLDOC01-appb-C000001
     ［式（１ｂ）中、Ｒ１Ｂは、水素原子またはメチル基を表し、
    　Ｒ２Ｂ～Ｒ４Ｂは、それぞれ独立に、水素原子、炭素数１～６のアルキル基または炭素数１～６のアルコキシ基を表し、
    　ｎは、１～１０の整数を表し、および
    　＊は、結合位置を表し、
    　但し、Ｒ２Ｂ～Ｒ４Ｂの少なくとも一つは、炭素数１～６のアルコキシ基である。］
    で表される構成単位（ｂ１－１）を含む樹脂（Ｂ１）を含む着色硬化性樹脂組成物。     A color curable resin composition containing a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).
    The color curable resin composition further contains a phenolic antioxidant (E).
    The resin (B) is the formula (1b):
    Figure JPOXMLDOC01-appb-C000001
     [In formula (1b), R 1B represents a hydrogen atom or a methyl group.
    R 2B to R 4B independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
    n represents an integer from 1 to 10, and * represents the bond position.
    However, at least one of R 2B to R 4B is an alkoxy group having 1 to 6 carbon atoms. ]
    A colored curable resin composition containing a resin (B1) containing a structural unit (b1-1) represented by.
  2. 　樹脂（Ｂ１）が、構成単位（ｂ１－１）、酸性基を有する重合性不飽和化合物に由来する構成単位（ｂ１－２）および他の構成単位（ｂ１－３）を含む共重合体であり、且つ共重合体中の全構成単位の合計を１００モル％としたときの構成単位（ｂ１－１）の量が、１～５０モル％である請求項１に記載の着色硬化性樹脂組成物。 The resin (B1) is a copolymer containing a structural unit (b1-1), a structural unit (b1-2) derived from a polymerizable unsaturated compound having an acidic group, and other structural units (b1-3). The colored curable resin composition according to claim 1, wherein the amount of the structural units (b1-1) is 1 to 50 mol% when the total of all the structural units in the copolymer is 100 mol%. ..
  3. 　樹脂（Ｂ１）の重量平均分子量が１，０００～５０，０００である請求項１または２に記載の着色硬化性樹脂組成物。 The colored curable resin composition according to claim 1 or 2, wherein the weight average molecular weight of the resin (B1) is 1,000 to 50,000.
  4. 　樹脂（Ｂ１）の含有量が、重合性化合物（Ｃ）１００重量部に対して５～４００重量部である請求項１～３のいずれか一項に記載の着色硬化性樹脂組成物。 The colored curable resin composition according to any one of claims 1 to 3, wherein the content of the resin (B1) is 5 to 400 parts by weight with respect to 100 parts by weight of the polymerizable compound (C).
  5. 　フェノール系酸化防止剤（Ｅ）の含有量が、重合性化合物（Ｃ）１００重量部に対して０．１～２５重量部である請求項１～４のいずれか一項に記載の着色硬化性樹脂組成物。 The color curability according to any one of claims 1 to 4, wherein the content of the phenolic antioxidant (E) is 0.1 to 25 parts by weight with respect to 100 parts by weight of the polymerizable compound (C). Resin composition.
  6. 　着色剤（Ａ）が、染料（Ａ１）および顔料（Ａ２）を含む請求項１～５のいずれか一項に記載の着色硬化性樹脂組成物。 The color-curable resin composition according to any one of claims 1 to 5, wherein the colorant (A) contains a dye (A1) and a pigment (A2).
  7. 　重合性化合物（Ｃ）が、ラジカル重合性化合物であり、且つ重合開始剤（Ｄ）が、光ラジカル重合開始剤である請求項１～６のいずれか一項に記載の着色硬化性樹脂組成物。 The colored curable resin composition according to any one of claims 1 to 6, wherein the polymerizable compound (C) is a radically polymerizable compound and the polymerization initiator (D) is a photoradical polymerization initiator. ..
  8. 　着色剤（Ａ）が、式（Ａ３－１）：
    Figure JPOXMLDOC01-appb-C000002
     ［式（Ａ３－１）中、Ｒ４１ａおよびＲ４２ａは、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１～２０の飽和炭化水素基、置換基を有していてもよい炭素数６～１４の芳香族炭化水素基、または置換基を有していてもよい炭素数７～３０のアラルキル基を表すか、或いはＲ４１ａとＲ４２ａとが結合して、それらが結合する窒素原子と共に３～１０員の含窒素複素環を形成し、
    　Ｒ４３ａおよびＲ４４ａは、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１～２０の飽和炭化水素基、置換基を有していてもよい炭素数６～１４の芳香族炭化水素基、または置換基を有していてもよい炭素数７～３０のアラルキル基を表すか、或いはＲ４３ａとＲ４４ａとが結合してそれらが結合する窒素原子と共に３～１０員の含窒素複素環を形成し、
    　Ｒ４７ａ～Ｒ５４ａは、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、ヒドロキシ基、－ＳＯ３ －、－ＳＯ２－Ｎ－－ＳＯ２－Ｒｆ、または置換基を有していてもよい炭素数１～８のアルキル基を表し、
    　Ｒｆは、炭素数１～１２のフルオロアルキル基を表し、
    　環Ｔ１ａは、置換基を有していてもよい炭素数６～１４の芳香族炭化水素環または置換基を有していてもよい５～１０員の芳香族複素環を表し、
    　前記炭素数１～２０の飽和炭化水素基が有していてもよい置換基は、ハロゲン原子、ヒドロキシ基、ホルミル基およびアミノ基からなる群から選ばれる少なくとも一つであり、
    　前記炭素数６～１４の芳香族炭化水素基が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、－ＳＯ３ －、－ＳＯ２－Ｎ－－ＳＯ２－Ｒｆ、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つであり、
    　前記炭素数７～３０のアラルキル基が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、－ＳＯ３ －、－ＳＯ２－Ｎ－－ＳＯ２－Ｒｆ、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つであり、
    　前記炭素数６～１４の芳香族炭化水素環が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、－ＳＯ３ －、－ＳＯ２－Ｎ－－ＳＯ２－Ｒｆ、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つであり、
    　前記５～１０員の芳香族複素環が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、－ＳＯ３ －、－ＳＯ２－Ｎ－－ＳＯ２－Ｒｆ、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つであり、
    　前記炭素数１～８のアルキル基が有していてもよい置換基は、ハロゲン原子、ヒドロキシ基、ホルミル基およびアミノ基からなる群から選ばれる少なくとも一つであり、
    　前記炭素数１～２０の飽和炭化水素基が炭素数２～２０の飽和炭化水素基である場合、前記飽和炭化水素基に含まれる－ＣＨ２－は、－Ｏ－または－ＣＯ－に置き換わっていてもよく、
    　前記炭素数１～８のアルキル基が炭素数２～８のアルキル基である場合、前記アルキル基に含まれる－ＣＨ２－は、－Ｏ－または－ＣＯ－に置き換わっていてもよく、
    　ｒは、１以上の整数を表し、
    　Ｍｒ＋は、水素イオン、ｒ価の金属イオンまたはＮ＋（Ｒ５５ａ）４を表し、四つのＲ５５ａは同一でも、異なっていてもよく、
    　Ｒ５５ａは、水素原子、炭素数１～２０の飽和炭化水素基または炭素数７～１０のアラルキル基を表し、
    　ｋは、式（Ａ３－１ａ）：
    Figure JPOXMLDOC01-appb-C000003
     ［式（Ａ３－１ａ）中、環Ｔ１ａ、Ｒ４１ａ～Ｒ４４ａおよびＲ４７ａ～Ｒ５４ａは、それぞれ、上記と同義である。］
    で表されるアニオンが有する－ＳＯ３ －および－ＳＯ２－Ｎ－－ＳＯ２－Ｒｆの個数の合計を表し、且つ２以上の整数であり、
    　ｒが２以上の整数である場合、式（Ａ３－１ａ）で表される複数のアニオンは、同一でも、異なっていてもよく、並びに
    　ｋ－１が２以上の整数である場合、複数のＭｒ＋は、同一でも、異なっていてもよい。］
    で表される化合物、および
    　式（Ａ３－２）：
    Figure JPOXMLDOC01-appb-C000004
     ［式（Ａ３－２）中、Ｒ４１ｂおよびＲ４２ｂは、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１～２０の飽和炭化水素基、置換基を有していてもよい炭素数６～
    １４の芳香族炭化水素基、または置換基を有していてもよい炭素数７～３０のアラルキル基を表すか、或いはＲ４１ｂとＲ４２ｂとが結合して、それらが結合する窒素原子と共に３～１０員の含窒素複素環を形成し、
    　Ｒ４３ｂおよびＲ４４ｂは、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１～２０の飽和炭化水素基、置換基を有していてもよい炭素数６～１４の芳香族炭化水素基、または置換基を有していてもよい炭素数７～３０のアラルキル基を表すか、或いはＲ４３ｂとＲ４４ｂとが結合してそれらが結合する窒素原子と共に３～１０員の含窒素複素環を形成し、
    　Ｒ４７ｂ～Ｒ５４ｂは、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、ヒドロキシ基、または置換基を有していてもよい炭素数１～８のアルキル基を表し、
    　環Ｔ１ｂは、置換基を有していてもよい炭素数６～１４の芳香族炭化水素環または置換基を有していてもよい５～１０員の芳香族複素環を表し、
    　前記炭素数１～２０の飽和炭化水素基が有していてもよい置換基は、ハロゲン原子、ヒドロキシ基、ホルミル基およびアミノ基からなる群から選ばれる少なくとも一つであり、
    　前記炭素数６～１４の芳香族炭化水素基が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つであり、
    　前記炭素数７～３０のアラルキル基が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つであり、
    　前記炭素数６～１４の芳香族炭化水素環が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つであり、
    　前記５～１０員の芳香族複素環が有していてもよい置換基は、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、および置換基を有していてもよい炭素数１～８のアルキル基からなる群から選ばれる少なくとも一つであり、
    　前記炭素数１～８のアルキル基が有していてもよい置換基は、ハロゲン原子、ヒドロキシ基、ホルミル基およびアミノ基からなる群から選ばれる少なくとも一つであり、
    　前記炭素数１～２０の飽和炭化水素基が炭素数２～２０の飽和炭化水素基である場合、前記飽和炭化水素基に含まれる－ＣＨ２－は、－Ｏ－または－ＣＯ－に置き換わっていてもよく、
    　前記炭素数１～８のアルキル基が炭素数２～８のアルキル基である場合、前記アルキル基に含まれる－ＣＨ２－は、－Ｏ－または－ＣＯ－に置き換わっていてもよく、
    　ｍは、１以上の整数を表し、
    　［Ｙ］ｍ－は、ｍ価のアニオンを表し、並びに
    　ｍが２以上の整数である場合、式（Ａ３－２ｃ）：
    Figure JPOXMLDOC01-appb-C000005
     ［式（Ａ３－２ｃ）中、環Ｔ１ｂ、Ｒ４１ｂ～Ｒ４４ｂおよびＲ４７ｂ～Ｒ５４ｂは、それぞれ、上記と同義である。］
    で表される複数のカチオンは、同一でも、異なっていてもよい。］
    で表される化合物からなる群から選ばれる少なくとも一つの化合物（Ａ３）を含む請求項１～７のいずれか一項に記載の着色硬化性樹脂組成物。     The colorant (A) has the formula (A3-1):
    Figure JPOXMLDOC01-appb-C000002
     [In the formula (A3-1), R 41a and R 42a each independently have a hydrogen atom and a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and a substituent. It represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R 41a and R 42a are bonded to each other. Form a 3- to 10-membered nitrogen-containing heterocycle with the nitrogen atom to which
    R 43a and R 44a each independently have a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and 6 to 14 carbon atoms which may have a substituent. It represents an aromatic hydrocarbon group, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or 3 to 10 members together with a nitrogen atom to which R 43a and R 44a are bonded and bonded to each other. Forming a nitrogen-containing heterocycle of
    R 47a ~ R 54a are each independently a hydrogen atom, a halogen atom, a nitro group, hydroxy group, -SO 3 -, -SO 2 -N - have -SO 2 -R f or a substituent, Represents a good alkyl group with 1 to 8 carbon atoms
    R f represents a fluoroalkyl group having 1 to 12 carbon atoms.
    Ring T 1a represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms which may have a substituent or a 5 to 10 member aromatic heterocycle which may have a substituent.
    The substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
    The aromatic hydrocarbon group substituents which may be possessed by the carbon number of 6 to 14, a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - -SO 2 - R f , and at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have a substituent.
    Substituents which may be the aralkyl group have the carbon number of 7 to 30, a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - -SO 2 -R f, And at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have substituents.
    Aromatic hydrocarbon ring substituent that have the carbon number of 6 to 14, a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - -SO 2 - R f , and at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have a substituent.
    Wherein said 5 to 10-membered aromatic heterocyclic ring substituent which may have of a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - -SO 2 -R f , And at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have substituents.
    The substituent which the alkyl group having 1 to 8 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
    When the saturated hydrocarbon group having 1 to 20 carbon atoms is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH 2- contained in the saturated hydrocarbon group is replaced with -O- or -CO-. May be
    When the alkyl group having 1 to 8 carbon atoms is an alkyl group having 2 to 8 carbon atoms, -CH 2- contained in the alkyl group may be replaced with -O- or -CO-.
    r represents an integer of 1 or more
    Mr + represents a hydrogen ion, an r-valent metal ion or N + (R 55a ) 4 , and the four R 55a may be the same or different.
    R 55a represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.
    k is the formula (A3-1a):
    Figure JPOXMLDOC01-appb-C000003
     [In the formula (A3-1a), the rings T 1a , R 41a to R 44a and R 47a to R 54a are synonymous with the above, respectively. ]
    In -SO 3 anion has represented - and -SO 2 -N - represents the total number of -SO 2 -R f, a and an integer of 2 or more,
    When r is an integer of 2 or more, the plurality of anions represented by the formula (A3-1a) may be the same or different, and when k-1 is an integer of 2 or more, a plurality of Ms. r + may be the same or different. ]
    The compound represented by, and the formula (A3-2):
    Figure JPOXMLDOC01-appb-C000004
     [In the formula (A3-2), R 41b and R 42b each independently have a hydrogen atom and a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent which may have a substituent. May have 6 to carbon atoms
    Represents an aromatic hydrocarbon group of 14 or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R 41b and R 42b are bonded and 3 together with the nitrogen atom to which they are bonded. Forming a nitrogen-containing heterocycle of ~ 10 members,
    R 43b and R 44b independently have a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and 6 to 14 carbon atoms which may have a substituent. It represents an aromatic hydrocarbon group, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or 3 to 10 members together with a nitrogen atom to which R 43b and R 44b are bonded and bonded to each other. Forming a nitrogen-containing heterocycle of
    R 47b to R 54b each independently represent an alkyl group having 1 to 8 carbon atoms which may have a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or a substituent.
    Ring T 1b represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms which may have a substituent or a 5 to 10 member aromatic heterocycle which may have a substituent.
    The substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
    The substituents that the aromatic hydrocarbon group having 6 to 14 carbon atoms may have may have a halogen atom, a nitro group, a hydroxy group, a formyl group, and a substituent having 1 to 8 carbon atoms. At least one selected from the group consisting of alkyl groups of
    The substituents that the aralkyl group having 7 to 30 carbon atoms may have are a halogen atom, a nitro group, a hydroxy group, a formyl group, and an alkyl group having 1 to 8 carbon atoms that may have a substituent. At least one selected from the group consisting of
    The substituents that the aromatic hydrocarbon ring having 6 to 14 carbon atoms may have may have a halogen atom, a nitro group, a hydroxy group, a formyl group, and a substituent having 1 to 8 carbon atoms. At least one selected from the group consisting of alkyl groups of
    Substituents that the 5- to 10-membered aromatic heterocycle may have are halogen atoms, nitro groups, hydroxy groups, formyl groups, and alkyl having 1 to 8 carbon atoms that may have substituents. At least one selected from the group of groups,
    The substituent which the alkyl group having 1 to 8 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
    When the saturated hydrocarbon group having 1 to 20 carbon atoms is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH 2- contained in the saturated hydrocarbon group is replaced with -O- or -CO-. May be
    When the alkyl group having 1 to 8 carbon atoms is an alkyl group having 2 to 8 carbon atoms, -CH 2- contained in the alkyl group may be replaced with -O- or -CO-.
    m represents an integer of 1 or more
    [Y] m- represents an m-valent anion, and when m is an integer of 2 or more, the formula (A3-2c):
    Figure JPOXMLDOC01-appb-C000005
     [In the formula (A3-2c), rings T 1b , R 41b to R 44b and R 47b to R 54b are synonymous with the above, respectively. ]
    The plurality of cations represented by may be the same or different. ]
    The colored curable resin composition according to any one of claims 1 to 7, which comprises at least one compound (A3) selected from the group consisting of the compounds represented by.
  9. 　着色剤（Ａ）が、化合物（Ａ３）とは異なる染料（Ａ１）を含む請求項８に記載の着色硬化性樹脂組成物。 The color-curable resin composition according to claim 8, wherein the colorant (A) contains a dye (A1) different from that of the compound (A3).
PCT/JP2020/018102 2019-05-08 2020-04-28 Colored curable resin composition WO2020226099A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
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JP2021015279A (en) * 2019-07-10 2021-02-12 住華科技股▲フン▼有限公司Ｓｕｍｉｋａ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．，Ｌｔｄ Coloring resin composition and color filter and display device using the same
WO2023238762A1 (en) * 2022-06-10 2023-12-14 株式会社Ｄｎｐファインケミカル Method for producing blue cured film, blue photosensitive composition, color filter and method for producing same, and display device

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150315376A1 (en) * 2014-04-30 2015-11-05 Chi Mei Corporation Photosensitive resin composition for color filter and application thereof
JP2016145975A (en) * 2015-01-30 2016-08-12 住友化学株式会社 Colored photosensitive resin composition

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Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150315376A1 (en) * 2014-04-30 2015-11-05 Chi Mei Corporation Photosensitive resin composition for color filter and application thereof
JP2016145975A (en) * 2015-01-30 2016-08-12 住友化学株式会社 Colored photosensitive resin composition

Cited By (2)

* Cited by examiner, † Cited by third party
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JP2021015279A (en) * 2019-07-10 2021-02-12 住華科技股▲フン▼有限公司Ｓｕｍｉｋａ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．，Ｌｔｄ Coloring resin composition and color filter and display device using the same
WO2023238762A1 (en) * 2022-06-10 2023-12-14 株式会社Ｄｎｐファインケミカル Method for producing blue cured film, blue photosensitive composition, color filter and method for producing same, and display device

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