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WO2024190528A1 - Coloring curable resin composition, optical filter, and solid-state imaging element - Google Patents

Coloring curable resin composition, optical filter, and solid-state imaging element Download PDF

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Publication number
WO2024190528A1
WO2024190528A1 PCT/JP2024/008224 JP2024008224W WO2024190528A1 WO 2024190528 A1 WO2024190528 A1 WO 2024190528A1 JP 2024008224 W JP2024008224 W JP 2024008224W WO 2024190528 A1 WO2024190528 A1 WO 2024190528A1
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group
meth
carbon atoms
acrylate
mass
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PCT/JP2024/008224
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French (fr)
Japanese (ja)
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尚史 原
貴裕 黒木
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住友化学株式会社
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Publication of WO2024190528A1 publication Critical patent/WO2024190528A1/en

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    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
    • 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
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings
    • 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
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings
    • C08K5/3465—Six-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/28—Pyronines ; Xanthon, thioxanthon, selenoxanthan, telluroxanthon dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters

Definitions

  • the present invention relates to a colored curable resin composition, an optical filter, and a solid-state imaging device.
  • Optical filters used in displays such as liquid crystal displays, electroluminescent displays, and plasma displays, and solid-state imaging devices such as CCD and CMOS sensors, are manufactured from colored curable resin compositions (see, for example, Patent Document 1). It is also known that the color difference ( ⁇ E* ab ) after irradiation with light can be suppressed by adding a specific metal compound to the colored curable resin composition (Patent Documents 2 to 4).
  • An object of the present invention is to provide a colored curable resin composition capable of maintaining the absorbance at the maximum absorption wavelength.
  • a colored curable resin composition comprising a colorant, a resin, a polymerization initiator, a polymerizable compound, and a metal compound, wherein the metal compound comprises a compound represented by formula (I).
  • R A1 to R A6 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, an amino group, a nitro group, a carboxyl group, a sulfo group, OR A7 , NHR A7 , or N(R A7 ) 2 , where R A7 represents a hydrocarbon group having 1 to 10 carbon atoms.
  • X A represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, an amino group, a nitro group, a carboxyl group, a sulfo group, OR A7 , NHR A7 , or N(R A7 ) 2 .
  • M A represents a metal atom of Groups 8 to 13
  • n is an integer of 1 to 3
  • the dotted line between M A and N represents a coordinate bond.
  • R 1 and R 2 may be joined together to form a ring containing a nitrogen atom, and R 3 and R 4 may be joined together to form a ring containing a nitrogen atom.
  • R5 represents -OH, -SO3- , -SO3H , -SO3 - Z + , -CO2H , -CO2 - Z + , -CO2R8 , -SO3R8 or -SO2NR9R10 .
  • 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 of 0 to 5. When m is 2 or more, multiple R5's may be the same or different.
  • a represents an integer of 0 or 1.
  • X represents a halogen atom.
  • Z + represents + N(R 11 ) 4 , Na + or K + , and the four R 11 s may be the same or different.
  • R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
  • R 9 and R 10 each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, in which -CH 2 - contained in the saturated aliphatic hydrocarbon group may be replaced by -O-, -CO-, -NH- or -NR 8 -, and R 9 and R 10 may bond to each other to form a 3- to 10-membered heterocycle containing a nitrogen atom.
  • 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.
  • the present invention it is possible to provide a colored curable resin composition capable of forming an optical filter capable of maintaining the absorbance at the maximum absorption wavelength. According to the present invention, it is also possible to suppress the color difference ( ⁇ E* ab ) for a longer period of time.
  • the colored curable resin composition of the present invention contains a colorant (hereinafter, may be referred to as colorant (A)), a resin (hereinafter, may be referred to as resin (B)), a polymerizable compound (hereinafter, may be referred to as polymerizable compound (C)), a polymerization initiator (hereinafter, may be referred to as polymerization initiator (D)), and a metal compound (hereinafter, may be referred to as metal compound (G)), and the metal compound contains a compound represented by formula (I).
  • the colored curable resin composition of the present invention may further contain a solvent (hereinafter, may be referred to as solvent (E)).
  • the colored curable resin composition of the present invention may further contain a polymerization initiation aid (hereinafter, may be referred to as polymerization initiation aid (D1)).
  • the colored curable resin composition of the present invention may further contain a thiol compound (hereinafter, may be referred to as thiol compound (T)).
  • the colored curable resin composition of the present invention may further contain a leveling agent (hereinafter, may be referred to as leveling agent (F)).
  • leveling agent hereinafter, may be referred to as leveling agent (F)
  • the compounds exemplified as each component may be used alone or in combination of two or more kinds, unless otherwise specified.
  • the metal compound (G) includes a compound represented by formula (I), and when used together with a colorant (preferably a compound represented by formula (II)), the absorbance at the maximum absorption wavelength can be maintained.
  • R A1 to R A6 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, an amino group, a nitro group, a carboxyl group, a sulfo group, OR A7 , NHR A7 , or N(R A7 ) 2 , where R A7 represents a hydrocarbon group having 1 to 10 carbon atoms.
  • X A represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, an amino group, a nitro group, a carboxyl group, a sulfo group, OR A7 , NHR A7 , or N(R A7 ) 2 .
  • M A represents a metal atom of Groups 8 to 13
  • n is an integer of 1 to 3
  • the dotted line between M A and N represents a coordinate bond.
  • Examples of the halogen atom represented by R A1 to R A6 and XA include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.
  • the hydrocarbon groups having 1 to 20 carbon atoms represented by R to R and X may be aliphatic hydrocarbon groups or aromatic hydrocarbon groups, and the aliphatic hydrocarbon groups may be saturated or unsaturated and may be linear or cyclic (alicyclic hydrocarbon groups).
  • Examples of the saturated or unsaturated chain hydrocarbon group represented by R A1 to R A6 and X A include straight-chain alkyl groups such as 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, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an icosyl group; Isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylbutyl group
  • the number of carbon atoms in the saturated chain hydrocarbon group (i.e., linear alkyl group, branched alkyl group) represented by R A1 to R A6 and XA is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 5.
  • the unsaturated chain hydrocarbon groups (that is, alkenyl groups, alkynyl groups) represented by R A1 to R A6 and X A preferably have 2-10 carbon atoms, more preferably 2-7 carbon atoms, and even more preferably 2-5 carbon atoms.
  • Examples of the saturated or unsaturated alicyclic hydrocarbon group represented by R A1 to R A6 and XA include a cyclopropyl group, a 1-methylcyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a 1-methylcyclohexyl group, a 2-methylcyclohexyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, a 1,2-dimethylcyclohexyl group, a 1,3-dimethylcyclohexyl group, a 1,4-dimethylcyclohexyl group, a 2,3-dimethylcyclohexyl group, a 2,4-dimethylcyclohexyl group, a 2,5-dimethylcyclohexyl group, a 2,6-dimethylcyclohexyl group, a 2,
  • Examples of the aromatic hydrocarbon group represented by R A1 to R A6 and XA include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2-ethylphenyl group, a 3-ethylphenyl group, a 4-ethylphenyl group, a 2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,6-dimethylphenyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 4-vinylphenyl group, an o-isopropylphenyl group, an m-isopropylphenyl group, a p-isopropylphenyl group, an o-tert-butylphenyl group, an m-tert-butylphenyl group,
  • the hydrocarbon groups represented by R to R and X may be a group obtained by combining the above-mentioned hydrocarbon groups (for example, an aromatic hydrocarbon group and at least one of a chain hydrocarbon group and an alicyclic hydrocarbon group), aralkyl groups such as a benzyl group, a (2-methylphenyl)methyl group, a (3-methylphenyl)methyl group, a (4-methylphenyl)methyl group, a (2-ethylphenyl)methyl group, a (3-ethylphenyl)methyl group, a (4-ethylphenyl)methyl group, a (2-(tert-butyl)phenyl)methyl group, a (3-(tert-butyl)phenyl)methyl group, a (4-(tert-butyl)phenyl)methyl group, a (3,5-dimethylphenyl)methyl group, a 1-phenylethyl group, a 1-methyl-1-phenylethyl
  • the groups represented by R to R and X may be groups combining the above-listed hydrocarbon groups (for example, a chain hydrocarbon group and an alicyclic hydrocarbon group), such as an alkyl group having one or more alicyclic hydrocarbon groups bonded thereto, such as a cyclopropylmethyl group, a cyclopropylethyl group, a cyclobutylmethyl group, a cyclobutylethyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, a (2-methylcyclohexyl)methyl group, a cyclohexylethyl group, or an adamantylmethyl group.
  • These preferably have 4 to 15 carbon atoms, and more preferably 4 to 10 carbon atoms.
  • Examples of the hydrocarbon group represented by R A7 include the same ones having 1 to 10 carbon atoms among the hydrocarbon groups having 1 to 20 carbon atoms represented by R A1 to R A6 and XA .
  • OR A7 represented by R A1 to R A6 and XA examples 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, a nonyloxy group, and a decyloxy group.
  • NHR represented by R to R and XA examples include an N-methylamino group, an N-ethylamino group, an N-propylamino group, an N-isopropylamino group, an N-butylamino group, an N-isobutylamino group, an N-sec-butylamino group, an N-tert-butylamino group, an N-pentylamino group, an N-(1-ethylpropyl)amino group, an N-hexylamino group, an N-(2-ethyl)hexylamino group, an N-heptylamino group, an N-octylamino group, an N-nonylamino group, an N-phenylamino group, and an N-decylamino group.
  • N(R A7 ) 2 represented by R A1 to R A6 and XA includes an N,N-dimethylamino group, an N,N-diethylamino group, an N,N-dipropylamino group, an N,N-diisopropylamino group, an N,N-dibutylamino group, an N,N-diisobutylamino group, an N,N-disec-butylamino group, an N,N-ditert-butylamino group, an N,N-dipentylamino group, an N,N-di(1-ethylpropyl)amino group, an N,N-dihexylamino group, an N,N-di(2-ethyl)
  • Examples of such an amino group include a hexylamino group, an N,N-diheptylamino group, an N,N-diphenylamino group, an
  • M A is a Group 8 to 13 metal atom.
  • metal atoms of Groups 8 to 13 represented by M A include Group 8 elements such as iron (Period 4), ruthenium (Period 5), and osmium (Period 6), Group 9 elements such as cobalt (Period 4), rhodium (Period 5), and iridium (Period 6), Group 10 elements such as nickel (Period 4), palladium (Period 5), and platinum (Period 6), and Group 10 elements such as copper (Period 4), silver (Period 5), and gold (Period 6).
  • Group 8 elements such as iron (Period 4), ruthenium (Period 5), and osmium (Period 6)
  • Group 9 elements such as cobalt (Period 4), rhodium (Period 5), and iridium (Period 6)
  • Group 10 elements
  • Group 11 elements such as zinc (4th period), cadmium (5th period), and mercury (6th period);
  • Group 12 elements such as aluminum (3rd period), gallium (4th period), indium (5th period), and thallium (6th period);
  • Group 13 elements such as aluminum (3rd period), gallium (4th period), indium (5th period), and thallium (6th period).
  • M A is preferably a metal atom of periods 4 to 5 in groups 8 to 13, more preferably a metal atom of periods 4 in groups 8 to 13, and even more preferably a copper atom.
  • n is an integer from 1 to 3, preferably 2 or 3, and more preferably 2.
  • m is an integer of 0 or more, preferably an integer of 0 or more and 10 or less, more preferably an integer of 0 or more and 5 or less, even more preferably an integer of 0 or more and 3 or less, even more preferably an integer of 0 or more and 1 or less, and particularly preferably 0.
  • R A1 to R A6 each independently preferably represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 15 carbon atoms, even more preferably a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, even more preferably a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and particularly preferably a hydrogen atom.
  • m is preferably 0, but may be equal to or greater than 1.
  • X A preferably represents a halogen atom, a hydroxy group, an amino group, or N(R A7 ) 2 .
  • the compounds represented by formula (I) include compounds represented by formulas (I-A1) to (I-A80), preferably compounds represented by formulas (I-A1) to (I-A60), and more preferably compounds represented by formulas (I-A1) to (I-A10).
  • the content of the compound represented by formula (I) is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 100% by mass, based on 100% by mass of the metal compound.
  • the content of the metal compound is preferably 0.1 to 75 parts by mass, more preferably 1 to 50 parts by mass, even more preferably 2 to 40 parts by mass, and even more preferably 3 to 30 parts by mass, per 100 parts by mass of the colorant.
  • the content of the metal compound is preferably 0.1 to 30 mass%, more preferably 0.5 to 20 mass%, even more preferably 1 to 15 mass%, and even more preferably 2 to 10 mass%, based on 100 mass% of the solid content of the colored curable resin composition.
  • the colorant (A) preferably contains a compound represented by formula (II). Even if the absorbance at the maximum absorption wavelength decreases when the compound represented by formula (II) is irradiated with light in the atmosphere, the decrease in absorbance can be suppressed by combining the compound represented by formula (II) with the metal compound specified in the present invention.
  • R 1 to R 4 each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group of 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group of 6 to 20 carbon atoms which may have a substituent, and -CH 2 - contained in the saturated hydrocarbon group may be replaced by -O-, -CO- or -NR 11 -.
  • R 1 and R 2 may be joined together to form a ring containing a nitrogen atom, and R 3 and R 4 may be joined together to form a ring containing a nitrogen atom.
  • R5 represents -OH, -SO3- , -SO3H , -SO3 - Z + , -CO2H , -CO2 - Z + , -CO2R8 , -SO3R8 or -SO2NR9R10 .
  • 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 of 0 to 5. When m is 2 or more, multiple R5's may be the same or different.
  • a represents an integer of 0 or 1.
  • X represents a halogen atom.
  • Z + represents + N(R 11 ) 4 , Na + or K + , and the four R 11 s may be the same or different.
  • R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
  • R 9 and R 10 each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, in which -CH 2 - contained in the saturated aliphatic hydrocarbon group may be replaced by -O-, -CO-, -NH- or -NR 8 -, and R 9 and R 10 may bond to each other to form a 3- to 10-membered heterocycle containing a nitrogen atom.
  • 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.
  • Examples of the monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms represented by R 1 to R 4 and R 8 to R 11 include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and icosyl groups; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl groups; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl groups.
  • linear alkyl groups such as methyl, ethyl, propyl, butyl, penty
  • Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R 1 to R 4 include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2-ethylphenyl group, a 3-ethylphenyl group, a 4-ethylphenyl group, a 2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,6-dimethylphenyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 4-vinylphenyl group, an o-isopropylphenyl group, an m-isopropylphenyl group, a p-isopropylphenyl group, an o-tert-butylphenyl group, an m-tert-butylphen
  • the substituent of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R 1 to R 4 may be a halogen atom, -OH, -OR 8 , -SO 3 - , -SO 3 H, -SO 3 - Z + , -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 --Z + is preferably --SO 3 -- + N(R 11 ) 4 .
  • R1 and R2 may form a ring containing a nitrogen atom together with the nitrogen atom
  • R3 and R4 may form a ring containing a nitrogen atom together with the nitrogen atom.
  • Examples of the ring containing a nitrogen atom 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, and an icosyloxycarbonyl group.
  • Examples of --SR 8 include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.
  • Examples of --SO 2 R 8 include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.
  • Examples of --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.
  • -SO 2 NR 9 R 10 is, for example, a sulfamoyl group; N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl 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-methylbut
  • the substituent of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R9 and R10 may be -OH or a halogen atom, and the -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, -NH- or -NR8- .
  • R 9 and R 10 may be bonded to each other to form a 3- to 10-membered heterocycle together with the nitrogen atom.
  • heterocycles include the following.
  • Examples of the alkyl group having 1 to 6 carbon atoms represented by R 6 and R 7 include the above-mentioned linear alkyl groups and branched alkyl groups having 1 to 6 carbon atoms.
  • Examples of the aralkyl group having 7 to 10 carbon atoms represented by R 11 include a benzyl group, a phenylethyl group, and a phenylbutyl group.
  • Z + is + N( R11 ) 4 , Na + or K + , preferably + N( R11 ) 4 .
  • the + N(R 11 ) 4 it is preferable that at least two of the four R 11 are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms.
  • the total number of carbon atoms of the four R 11 is preferably 20 to 80, and more preferably 20 to 60.
  • m is preferably 1 to 4, and more preferably 1 or 2.
  • the compound represented by formula (II) contains a compound represented by formula (IIa) (hereinafter sometimes referred to as "compound (IIa)").
  • R 21 to R 24 each independently represent a hydrogen atom or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.
  • R 21 and R 22 may form a ring containing a nitrogen atom together with the nitrogen atom, and R 23 and R 24 may form a ring containing a nitrogen atom together with the nitrogen atom.
  • R 25 represents --SO 3 -- , --SO 3 H, --SO 3 --Z1 + or --SO 2 NHR 26 .
  • m1 represents an integer of 0 to 5. When m1 is an integer of 2 or more, multiple R 25 may be the same or different.
  • a1 represents an integer of 0 or 1.
  • X1 represents a halogen atom.
  • R 26 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
  • Z1 + represents + N( R27 ) 4 , Na + or K + .
  • Each R 27 independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group.
  • Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R 21 to R 24 include the same groups as those exemplified as the aromatic hydrocarbon group for R 1 to R 4.
  • the substituent of the aromatic hydrocarbon group may be -SO 3 - , -SO 3 H, -SO 3 - Z1 + , -SO 3 R 26 or -SO 2 NHR 26 .
  • a preferred combination of R 21 to R 24 is one in which R 22 and R 23 are hydrogen atoms, R 21 and R 24 are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and R 25 is -SO 3 - , -SO 3 H, -SO 3 - Z1 + , -SO 3 R 26 , or -SO 2 NHR 26.
  • a more preferred combination is one in which R 22 and R 23 are hydrogen atoms, R 21 and R 24 are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and R 25 is -SO 3 - , -SO 3 - Z1 + , or -SO 2 NHR 26 .
  • R 21 and R 22 may be combined with the nitrogen atom to form an aliphatic heterocycle containing a nitrogen atom
  • R 23 and R 24 may be combined with the nitrogen atom to form an aliphatic heterocycle containing a nitrogen atom.
  • aliphatic heterocycle examples include the following:
  • Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 26 and R 27 include the same groups as those exemplified as the saturated hydrocarbon groups for R 8 to R 11 .
  • Z1 + is preferably + N( R27 ) 4 , Na + or K + , more preferably + N( R27 ) 4 .
  • the + N(R 27 ) 4 it is preferable that at least two of the four R 27 are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms.
  • the total number of carbon atoms of the four R 27 is preferably 20 to 80, and more preferably 20 to 60.
  • m1 is preferably 1 to 4, and more preferably 1 or 2.
  • Examples of the compound (IIa) include compounds represented by formulas (1-1) to (1-25).
  • R 26 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group.
  • a sulfonamide of C.I. Acid Red 289 a quaternary ammonium salt of C.I. Acid Red 289, a sulfonamide of C.I. Acid Violet 102, or a quaternary ammonium salt of C.I. Acid Violet 102 is preferred.
  • Examples of such compounds include compounds represented by formulas (1-1) to (1-8), (1-11), and (1-12).
  • compound (II) includes a compound represented by formula (IIIa) (hereinafter sometimes referred to as "compound (IIIa)").
  • R 32 and R 33 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 31 and R 34 each 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 32 may be taken together with the nitrogen atom to form a ring containing the nitrogen atom
  • R 33 and R 34 may be taken together with the nitrogen atom to form a ring containing the nitrogen atom.
  • p and q each independently represent an integer of 0 to 5. When p is 2 or more, multiple R 31 may be the same or different, and when q is 2 or more, multiple R 34 may be the same or different.
  • Examples of the alkyl group having 1 to 4 carbon atoms represented by R 31 , R 32 , 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 and a tert-butyl group.
  • Examples of the alkylsulfanyl group having 1 to 4 carbon atoms represented by R 31 and R 34 include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, and an isopropylsulfanyl group.
  • Examples of the alkylsulfonyl group having 1 to 4 carbon atoms represented by R 31 and R 34 include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group.
  • R 32 and R 33 are each preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • R 31 and R 34 are each preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.
  • p and q each independently represent preferably an integer of 0 to 2, and more preferably 1 or 2.
  • Examples of compound (IIIa) include compounds represented by formulas (1-26) to (1-36). Among them, compounds represented by formulas (1-26) to (1-32) and (1-36) are preferred because of their excellent solubility in organic solvents, and the compound represented by formula (1-36) (hereinafter also referred to as the compound represented by formula (II-1)) is more preferred.
  • the colorant (A) may contain a colorant different from the compound represented by formula (II).
  • the different colorants include dye (A1) and pigment (A2), and the pigment (A2) is preferred. These may be used alone or in combination of two or more.
  • the dye (A1) is not particularly limited, and known dyes can be used, such as solvent dyes, acid dyes, direct dyes, and mordant dyes.
  • dyes include compounds classified as dyes in the Color Index (published by The Society of Dyers and Colourists) and known dyes described in Dyeing Notes (Shikisensha).
  • examples of dyes that can be used according to their chemical structure include azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, phthalocyanine dyes, perylene dyes, quinophthalone dyes, and isoindoline dyes.
  • organic solvent-soluble dyes are preferred.
  • dyes having the following Color Index (C.I.) numbers are included.
  • C.I. Color Index
  • Solvent Orange 2 7, 11, 15, 26, 41, 54, 56, 77, 86, 99; C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; C.I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 38, 44, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; C.I. Solvent dyes such as C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35; C.I.
  • Acid dyes such as C. I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109; 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 dyes such as C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82; C.I. Disperse Yellow 51, 54, 76; C.I. Disperse Violet 26, 27; C.I. Disperse dyes such as C.I. Disperse Blue 1, 14, 56, 6;0, C.I. Basic Red 1, 10; C.I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89; C.I. Basic Violet 2; C.I. Basic Red 9; C.I.
  • Basic dyes such as C.I. Basic Green 1; C.I. Reactive Yellow 2, 76, 116; C.I. Reactive Orange 16; C.I. Reactive dyes such as C.I. Reactive Red 36; C.I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; C.I. Mordant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95; C.I.
  • These dyes can be selected appropriately to match the optical spectrum of the desired optical filter.
  • Pigments (A2) may be any known pigment, including, for example, pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists).
  • examples include azo pigments, cyanine pigments, triphenylmethane pigments, xanthene pigments, anthraquinone pigments, naphthoquinone pigments, quinoneimine pigments, methine pigments, azomethine pigments, squarylium pigments, acridine pigments, styryl pigments, coumarin pigments, quinoline pigments, nitro pigments, phthalocyanine pigments, perylene pigments, quinophthalone pigments, and isoindoline pigments. Of these, phthalocyanine pigments, quinophthalone pigments, and isoindoline pigments are preferred.
  • pigments classified as C.I. Pigment include yellow pigments such as 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, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, and 231; Orange pigments such as C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; red pigments such as C.I.
  • These pigments can be selected appropriately to match the optical spectrum of the desired optical filter.
  • the content of the compound represented by formula (II) in the total amount of the colorant is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 100% by mass.
  • a colorant-containing liquid containing the colorant (A) and the solvent (E) may be prepared in advance, and then the colorant-containing liquid may be used to prepare the colored curable resin composition.
  • the colorant (A) is not soluble in the solvent (E), for example when the colorant (A) contains a pigment (A2)
  • the colorant-containing liquid can be prepared by dispersing the colorant (A) in the solvent (E) and mixing.
  • the colorant-containing liquid may contain a part or all of the solvent (E) contained in the colored curable resin composition.
  • the solid content in the colorant-containing liquid is less than 100% by mass, preferably 1% by mass to 80% by mass, more preferably 2% by mass to 70% by mass, and even more preferably 5% by mass to 65% by mass, based on the total amount of the colorant-containing liquid.
  • the content of colorant (A) in the colorant-containing liquid is less than 100% by mass, preferably 0.5% by mass to 80% by mass, more preferably 1% by mass to 70% by mass, and even more preferably 2.5% by mass to 65% by mass, based on the total amount of solids in the colorant-containing liquid.
  • the colorant (A) may be subjected to a rosin treatment, a surface treatment using a derivative having an acidic or basic group introduced therein, a grafting treatment to the surface of the colorant (A) using a polymer compound, a micronization treatment using a sulfuric acid micronization method or a salt milling method, a washing treatment using an organic solvent or water to remove impurities, a removal treatment using an ion exchange method for ionic impurities, etc. It is preferable that the particle size of the colorant (A) is approximately uniform.
  • the colorant (A) can be made to be uniformly dispersed in the solution by adding a dispersant and carrying out a dispersion treatment.
  • a dispersant When using a combination of two or more types of colorant (A), each may be dispersed alone, or multiple types may be mixed and dispersed.
  • the dispersant may be, for example, a surfactant, which may be any of cationic, anionic, nonionic, and amphoteric surfactants. Specific examples include polyester, polyamine, and acrylic surfactants. These dispersants may be used alone or in combination of two or more.
  • dispersants by trade name examples include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLORENE (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Corporation), EFKA (registered trademark) (manufactured by BASF), AJISPER (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), and BYK (registered trademark) (manufactured by BYK-Chemie Co., Ltd.). Resin (B), which will be described later, may also be used as the dispersant.
  • KP manufactured by Shin-Etsu Chemical Co., Ltd.
  • FLORENE manufactured by Kyoeisha Chemical Co., Ltd.
  • Solsperse registered trademark
  • the amount of the dispersant (solid content) used is usually 1 part by mass to 10,000 parts by mass, preferably 5 parts by mass to 5,000 parts by mass, more preferably 10 parts by mass to 1,000 parts by mass, and even more preferably 15 parts by mass to 800 parts by mass, per 100 parts by mass of colorant (A) in the colorant-containing liquid.
  • a colorant-containing liquid hereinafter sometimes referred to as a colorant dispersion or pigment dispersion
  • the colorant-containing liquid may already contain a part or all, preferably a part, of the resin (B) contained in the colored curable resin composition.
  • the resin (B) By including the resin (B) in advance, the dispersion stability of the colorant-containing liquid can be further improved.
  • the content of resin (B) is, for example, 10 parts by mass or more and 10,000 parts by mass or less, preferably 20 parts by mass or more and 5,000 parts by mass or less, and more preferably 25 parts by mass or more and 2,500 parts by mass or less, relative to 100 parts by mass of colorant (A) in the colorant-containing liquid.
  • the content of the colorant (A) is preferably 1% by mass or more and 93% by mass or less, more preferably 10% by mass or more and 91% by mass or less, even more preferably 15% by mass or more and 89% by mass or less, and even more preferably 18% by mass or more and 87% by mass or less, based on the total amount of solids in the colored curable resin composition.
  • the content of the colorant (A) is within the above range, the color density when made into an optical filter is sufficient, and the necessary amount of the resin (B) can be contained in the composition, so that a pattern with sufficient mechanical strength can be formed, which is preferable.
  • total amount of solids in this specification refers to the amount obtained by subtracting the content of the solvent from the total amount of the colored curable resin composition.
  • the total amount of solids and the content of each component relative thereto can be measured by a known analytical means such as liquid chromatography or gas chromatography.
  • Resin [K1] a copolymer having a structural unit derived from at least one monomer (a) (hereinafter sometimes referred to as "(a)”) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a structural unit derived from a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond;
  • Resin [K2] a copolymer having a structural unit derived from the (a), a structural unit derived from the (b), and a structural unit derived from a monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter, may be referred to as "(c)”);
  • Resin [K3] a copolymer having a structural unit derived from the (a) and a structural unit derived from
  • (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; Unsaturated dicarboxylic acids such as 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, dimethyltetrahydrophthalic acid, and 1,4-cyclohexenedicarboxylic acid; Bicyclounsaturated compounds containing a carboxy group, such as methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]h
  • (b) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond.
  • (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.
  • (meth)acrylic acid refers to at least one selected from the group consisting of acrylic acid and methacrylic acid.
  • the terms "(meth)acryloyl" and “(meth)acrylate” have the same meaning.
  • Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)”), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b2)”), and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)”), etc.
  • a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond hereinafter sometimes referred to as "(b1)
  • a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond hereinafter sometimes referred to as "(b2)
  • Examples of (b1) include monomer (b1-1) (hereinafter sometimes referred to as "(b1-1)”) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, and monomer (b1-2) (hereinafter sometimes referred to as "(b1-2)”) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized.
  • (b1-1) includes glycidyl (meth)acrylate, ⁇ -methyl glycidyl (meth)acrylate, ⁇ -ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, ⁇ -methyl-o-vinylbenzyl glycidyl ether, ⁇ -methyl-m-vinylbenzyl glycidyl ether, ⁇ -methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyl Examples of such styrene include 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyl
  • (b1-2) includes vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Corporation), compounds represented by formula (BI) and compounds represented by formula (BII).
  • 1,2-epoxy-4-vinylcyclohexane e.g., Celloxide 2000; manufactured by Daicel Corporation
  • 3,4-epoxycyclohexylmethyl (meth)acrylate e.g., Cyclomer A400; manufactured by Daicel Corporation
  • 3,4-epoxycyclohexylmethyl (meth)acrylate e.g., Cyclomer M100; manufactured by Daicel
  • R e and R f represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group.
  • X e and X f each represent a single bond, *-R g -, *-R g -O-, *-R g -S- or *-R g -NH-.
  • R g represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond to O.
  • alkyl group having 1 to 4 carbon atoms examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
  • Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxy group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
  • R e and R f are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.
  • alkanediyl group examples include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group.
  • X e and X f are preferably a single bond, a methylene group, an ethylene group, *-CH 2 -O-, and *-CH 2 CH 2 -O-, and more preferably a single bond or *-CH 2 CH 2 -O- (* represents a bond to O).
  • the compound represented by formula (BI) includes compounds represented by any of formulas (BI-1) to (BI-15). Among them, compounds represented by formulas (BI-1), (BI-3), (BII-5), (BI-7), (BI-9) or (BI-11) to (BI-15) are preferred, and compounds represented by formulas (BI-1), (BI-7), (BI-9) or (BI-15) are more preferred.
  • the compound represented by formula (BII) includes compounds represented by any of formulas (BII-1) to (BII-15). Among them, compounds represented by formulas (BII-1), (BII-3), (BII-5), (BII-7), (BII-9) or (BII-11) to (BII-15) are preferred, and compounds represented by formulas (BII-1), (BII-7), (BII-9) or (BII-15) are more preferred.
  • the compound represented by formula (BI) and the compound represented by formula (BII) may be used alone or in combination of two or more kinds.
  • the content ratio thereof [compound represented by formula (BI): compound represented by formula (BII)] is preferably 5:95 to 95:5, more preferably 20:80 to 80:20 on a molar basis.
  • (b2) is a monomer having an oxetanyl group and a (meth)acryloyloxy group.
  • Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, and the like.
  • (b3) a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable.
  • Specific examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, etc.
  • (b1) is preferable since it can improve the reliability of the heat resistance, chemical resistance, etc. of the obtained optical filter. Furthermore, (b1-2) is more preferable since it provides excellent storage stability of the colored curable resin composition.
  • Examples of (c) include (meth)acrylic acid ester monomers, unsaturated carboxylates such as unsaturated dicarboxylates, and vinyl monomers having an unsaturated aliphatic hydrocarbon ring, an unsaturated heterocycle, or an aromatic ring.
  • Examples of (meth)acrylic acid ester monomers include (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group, such as 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, and cyclopentyl (meth)acrylate; (meth)acrylic acid esters having a linear or branched aliphatic unsaturated hydrocarbon group, such as allyl (meth)acrylate and propargyl (meth)acrylate; (meth)acrylic acid esters having a cyclic saturated hydrocarbon group, such as cyclohexyl (meth)acrylate, 2-methyl
  • C 1-10 alkyl (meth)acrylates such as methyl methacrylate and 2-ethylhexyl acrylate;
  • (meth)acrylic acid esters having a cyclic saturated hydrocarbon group such as tricyclo[5.2.1.0 2,6 ]decan-8-yl(meth)acrylate;
  • (meth)acrylic acid esters having a cyclic unsaturated aliphatic hydrocarbon group such as tricyclo[5.2.1.0 2,6 ]decene-8-yl (meth)acrylate;
  • vinyl monomers having an unsaturated aliphatic hydrocarbon ring examples include bicyclo[2.2.1]hept-2-ene (also called 2-norbornene), 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'-hydroxy 5,6-di(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
  • vinyl monomers having an unsaturated heterocycle include dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide.
  • dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimid
  • vinyl monomers having an aromatic ring examples include styrene-based monomers such as styrene, ⁇ -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene.
  • Other vinyl monomers include nitrile group-containing monomers such as acrylonitrile and methacrylonitrile; Halogen atom-containing monomers such as vinyl chloride and vinylidene chloride; Examples of the monomer include acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.
  • styrene-based monomers such as styrene and vinyltoluene
  • dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide and N-benzylmaleimide
  • bicyclo unsaturated compounds such as bicyclo[2.2.1]hept-2-ene (also called 2-norbornene) are preferred.
  • the structural unit obtained by adding (b) to a structural unit derived from (a) refers to a unit formed by bonding (b) by addition to a structural unit derived from (a) constituting the main chain of the copolymer, and has a pendant unsaturated group derived from (b).
  • (a) may be any of the above-mentioned examples, and (b) may also be any of the above-mentioned examples.
  • an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferable.
  • a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond is preferable, and a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is more preferable.
  • the structural unit obtained by adding (a) to a structural unit derived from (b) refers to a unit formed by bonding (a) by addition to a structural unit derived from (b) constituting the main chain of the copolymer, and has a pendant unsaturated group derived from (a).
  • (b) may be any of the above-mentioned examples, and (a) may also be any of the above-mentioned examples.
  • a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond is preferable, and a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is more preferable.
  • an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferable.
  • the structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic anhydride refers to a structural unit obtained by half-esterification of a carboxylic anhydride to a hydroxyl group generated by adding (a) to a structural unit derived from (b) constituting the main chain of the copolymer, and has a pendant carboxyl group derived from the carboxylic anhydride and a pendant unsaturated group derived from (a).
  • (b) may be any of the above-mentioned examples, and (a) may also be any of the above-mentioned examples.
  • a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond is preferable, and a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is more preferable.
  • an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferable.
  • carboxylic acid anhydride examples include saturated aliphatic polycarboxylic acid anhydrides such as malonic anhydride, succinic anhydride, glutaric anhydride, and adipic anhydride; unsaturated aliphatic polycarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, and itaconic anhydride; aromatic polycarboxylic acid anhydrides such as 3-vinylphthalic anhydride and 4-vinylphthalic anhydride; and alicyclic polycarboxylic acid anhydrides such as 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride.
  • saturated aliphatic polycarboxylic acid anhydrides such as malonic anhydride, succinic anhydride, glutaric anhydride, and adip
  • the ratio of the structural units derived from each of them to all the structural units constituting the resin [K1] is as follows: Structural units derived from (a): 2 to 60 mol% Structural units derived from (b): 40 to 98 mol% It is preferred that Structural units derived from (a): 10 to 50 mol % Structural units derived from (b): 50 to 90 mol% It is more preferable that: It is also preferred that the copolymer is substantially free of structural units derived from (c).
  • the total of the structural units derived from (a) and the structural units derived from (b) is, for example, 90 mol % or more, preferably 95 mol % or more, more preferably 98 mol % or more, and particularly preferably 100 mol % of all the structural units constituting the resin [K1].
  • the ratio of the structural units of the resin [K1] is within the above range, the colored curable resin composition tends to have excellent storage stability, developability when forming a colored pattern, and solvent resistance of the obtained optical filter.
  • Resin [K1] can be produced, for example, by referring to the method described in the literature "Experimental Methods for Polymer Synthesis” (written by Otsu Takayuki, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, published March 1, 1972) and the references cited in said literature.
  • Specific examples include a method in which predetermined amounts of (a) and (b), a polymerization initiator, a solvent, etc. are placed in a reaction vessel, and the atmosphere is deoxygenated, for example by replacing oxygen with nitrogen, and the mixture is heated and kept warm while stirring.
  • the polymerization initiator and solvent used here are not particularly limited, and those commonly used in the field can be used.
  • polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.), and the solvent may be any that dissolves each monomer, such as the solvent (E) described below for the colored curable resin composition of the present invention.
  • the copolymer obtained may be used as it is in the solution after the reaction, or may be a concentrated or diluted solution, or may be extracted as a solid (powder) by a method such as reprecipitation.
  • a solvent contained in the colored curable resin composition of the present invention as the solvent during this polymerization, the solution after the reaction can be used as it is in the preparation of the colored curable resin composition of the present invention, and the manufacturing process of the colored curable resin composition of the present invention can be simplified.
  • the ratio of the structural units derived from each of them to all the structural units constituting the resin [K2] is as follows: Structural units derived from (a): 1 to 70 mol% Structural units derived from (b): 1 to 60 mol% Structural units derived from (c): 20 to 95 mol% It is preferred that Structural units derived from (a): 3 to 50 mol % Structural units derived from (b): 3 to 40 mol% Structural units derived from (c): 30 to 90 mol% It is more preferable that Structural units derived from (a): 5 to 40 mol% Structural units derived from (b): 5 to 30 mol % Structural units derived from (c): 40 to 80 mol% It is even more preferred that: The total of the structural units derived from (a), the structural units derived from (b), and the structural units derived from (c) is, for example, 90
  • the colored curable resin composition tends to have excellent storage stability, developability when forming a colored pattern, and the obtained optical filter tends to have excellent solvent resistance, heat resistance, and mechanical strength.
  • (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid.
  • a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond is preferred, and a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized is more preferred.
  • (c)acrylic acid esters having a cyclic unsaturated aliphatic hydrocarbon group, (meth)acrylic acid esters having an aromatic ring, and dicarbonyl imide derivatives are preferred.
  • Resin [K2] can be produced, for example, in the same manner as described above for producing resin [K1].
  • the ratio of the structural units derived from each of them to all the structural units constituting the resin [K3] is as follows: Structural units derived from (a): 2 to 60 mol% Structural units derived from (c): 40 to 98 mol% It is preferred that Structural units derived from (a): 10 to 50 mol % Structural units derived from (c): 50 to 90 mol% It is more preferable that Structural units derived from (a): 35 to 45 mol% Structural units derived from (c): 55 to 65 mol% It is even more preferred that: It is also preferred that the copolymer is substantially free of structural units derived from (b).
  • the total of the structural units derived from (a) and the structural units derived from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% of all the structural units constituting the resin [K3].
  • Resin [K3] (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid, and (c) is preferably a (meth)acrylic acid ester having an aromatic ring.
  • Resin [K3] can be produced, for example, in the same manner as described above for producing resin [K1].
  • the ratio of the structural units derived from each of them to all the structural units constituting the resin [K4] is as follows: Structural units derived from (a) (without (b) added): 1 to 60 mol% Structural units obtained by adding (b) to a structural unit derived from (a): 1 to 50 mol % Structural units derived from (c): 30 to 90 mol% It is preferred that Structural units derived from (a) (without (b) added): 5 to 50 mol % Structural units obtained by adding (b) to a structural unit derived from (a): 5 to 40 mol% Structural units derived from (c): 35 to 80 mol% It is more preferable that Structural units derived from (a) (without (b) added): 10 to 40 mol% Structural units obtained by adding (b) to a structural unit derived from (a): 10 to 25 mol% Structural units derived from (
  • a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred.
  • a structural unit in which (b) is added to a structural unit derived from (a) a structural unit in which a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is added to a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred.
  • one or more types selected from (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group, (meth)acrylic acid esters having a cyclic saturated hydrocarbon group, (meth)acrylic acid esters having an aromatic ring, bicyclo unsaturated compounds, and styrene-based monomers are preferred, and two or more types are more preferred.
  • (c) has two types of structural units derived from it, it is preferable to select two types from unsaturated carboxylic acid esters such as (meth)acrylic acid esters, (meth)acrylic acid esters having a cyclic saturated hydrocarbon group, and (meth)acrylic acid esters having an aromatic ring, and to select two or more types from bicyclo unsaturated compounds and vinyl monomers such as styrene-based monomers.
  • unsaturated carboxylic acid esters such as (meth)acrylic acid esters, (meth)acrylic acid esters having a cyclic saturated hydrocarbon group, and (meth)acrylic acid esters having an aromatic ring
  • bicyclo unsaturated compounds and vinyl monomers such as styrene-based monomers.
  • Resin [K4] can be produced by obtaining a copolymer of (a) and (c), and adding the cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and/or carboxylic acid anhydride contained in (a).
  • a copolymer of (a) and (c) is produced in the same manner as described for the production method of resin [K1].
  • the ratio of the structural units derived from each is preferably the same as that described for resin [K3].
  • a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms contained in (b).
  • the atmosphere in the flask is replaced with air from nitrogen, and (b) a catalyst for the reaction of a carboxylic acid or a carboxylic acid anhydride with a cyclic ether (e.g., tris(dimethylaminomethyl)phenol, etc.), a polymerization inhibitor (e.g., hydroquinone, etc.), etc.
  • the amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, relative to 100 mol of (a). By using this range, the storage stability of the colored curable resin composition, the developability when forming a pattern, and the balance of the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern tend to be good.
  • the amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c).
  • the amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c).
  • the reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, etc.
  • the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, etc.
  • the ratio of the structural units derived from each of them to all the structural units constituting the resin [K4'] is as follows: Structural units obtained by adding (b) to a structural unit derived from (a): 5 to 95 mol% Structural units derived from (c): 5 to 95 mol% It is preferred that Structural units obtained by adding (b) to a structural unit derived from (a): 15 to 90 mol% Structural units derived from (c): 10 to 85 mol% It is more preferable that Structural units obtained by adding (b) to a structural unit derived from (a): 20 to 80 mol% Structural units derived from (c): 20 to 80 mol% It is even more preferred that: Furthermore, structural units derived from (a) to which (b) has not been added are substantially not included.
  • the sum of the structural unit obtained by adding (b) to the structural unit derived from (a) and the structural unit derived from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% of all structural units constituting the resin [K5'].
  • the structural unit obtained by adding (b) to a structural unit derived from (a) is preferably a structural unit obtained by adding a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized to a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid.
  • the structural unit derived from (c) is preferably one or more selected from (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group and (meth)acrylic acid esters having a cyclic saturated hydrocarbon group, more preferably two or more.
  • Resin [K4'] may be produced by referring to the production method of resin [K4] described above, and the amount of (b) used is preferably 100 mol per 100 mol of (a).
  • the ratio of the structural units derived from each of them to all the structural units constituting the resin [K5] is as follows: Structural units derived from (b) ((a) is not added): 0 to 30 mol% Structural units obtained by adding (a) to a structural unit derived from (b): 5 to 95 mol% Structural units derived from (c): 5 to 95 mol% It is preferred that Structural units derived from (b) ((a) is not added): 0 to 10 mol% Structural units obtained by adding (a) to a structural unit derived from (b): 15 to 90 mol% Structural units derived from (c): 10 to 85 mol% It is more preferable that Structural units derived from (b) ((a) is not added): 0 to 5 mol% Structural units obtained by adding (a) to a structural unit derived from (b): 20 to 80 mol% Structural units
  • a structural unit derived from (b) (without (a) added) a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is preferred.
  • a structural unit in which (a) is added to a structural unit derived from (b) a structural unit in which an unsaturated monocarboxylic acid such as (meth)acrylic acid is added to a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is preferred.
  • one or more types selected from (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group and (meth)acrylic acid esters having a cyclic saturated hydrocarbon group are preferred, and two or more types are more preferred.
  • Resin [K5] is produced in the first step by the same method as that for producing resin [K1] described above, to obtain a copolymer of (b) and (c).
  • the copolymer obtained may be used as it is in the form of a solution after the reaction, or may be a concentrated or diluted solution, or may be extracted as a solid (powder) by a method such as reprecipitation.
  • the ratios of the structural units derived from (b) and (c) to the total number of moles of all structural units constituting the copolymer are, respectively, Structural units derived from (b): 5 to 95 mol% Structural units derived from (c): 5 to 95 mol% It is preferred that Structural units derived from (b): 10 to 90 mol% Structural units derived from (c): 10 to 90 mol% It is more preferable that:
  • resin [K5] can be obtained by reacting a cyclic ether derived from (b) contained in a copolymer of (b) and (c) with a carboxylic acid or carboxylic acid anhydride contained in (a).
  • the amount of (a) to be reacted with the copolymer is preferably 5 to 100 moles per 100 moles of (b). Because the reactivity of cyclic ethers is high and unreacted (b) is unlikely to remain, (b1) is preferred as (b) for use in resin [K5], and (b1-1) is more preferred.
  • the ratio of the structural units derived from each of them to all the structural units constituting the resin [K6] is as follows: Structural units derived from (b) ((a) is not added): 0 to 30 mol% Structural units in which (a) is added to a structural unit derived from (b) (no carboxylic anhydride is added): 20 to 85 mol% A structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic acid anhydride thereto: 2 to 40 mol % Structural units derived from (c): 10 to 60 mol% It is preferred that Structural units derived from (b) ((a) is not added): 0 to 10 mol% Structural units in which (a) is added to a structural unit derived from (b) (no carboxylic anhydride is added): 40 to 80 mol% A structural unit obtained by adding (a) to a structural unit derived from
  • a structural unit derived from (b) (without (a) added a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is preferred.
  • a structural unit in which (a) is added to a structural unit derived from (b) (without carboxylic anhydride added) a structural unit in which an unsaturated monocarboxylic acid such as (meth)acrylic acid is added to a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is preferred.
  • a structural unit in which (a) is added to a structural unit derived from (b) and a carboxylic anhydride is further added a structural unit in which an unsaturated monocarboxylic acid such as (meth)acrylic acid is added to a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized and a saturated aliphatic polycarboxylic anhydride such as succinic anhydride is further added.
  • one or more types selected from (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group and (meth)acrylic acid esters having a cyclic saturated hydrocarbon group are preferred, and two or more types are more preferred.
  • Resin [K6] is produced in the first step by the same method as that for producing resin [K1] described above, to obtain a copolymer of (b) and (c).
  • the copolymer obtained may be used as it is in the form of a solution after the reaction, or a concentrated or diluted solution, or may be extracted as a solid (powder) by a method such as reprecipitation.
  • the ratios of the structural units derived from (b) and (c) to the total number of moles of all structural units constituting the copolymer are, respectively, Structural units derived from (b): 5 to 95 mol% Structural units derived from (c): 5 to 95 mol% It is preferred that Structural units derived from (b): 10 to 90 mol% Structural units derived from (c): 10 to 90 mol% It is more preferable that:
  • the cyclic ether derived from (b) contained in the copolymer of (b) and (c) is reacted with the carboxylic acid or carboxylic anhydride contained in (a).
  • the amount of (a) used is preferably 80 to 100 moles per 100 moles of (b).
  • the hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or carboxylic acid anhydride contained in (a) is reacted with the carboxylic acid anhydride.
  • the amount of the carboxylic acid anhydride used is preferably 0.05 to 1 mol, more preferably 0.10 to 0.8 mol, and even more preferably 0.13 to 0.7 mol, relative to 1 mol of the amount of (a) used (in other words, 1 mol of hydroxy groups generated by the use of (a)).
  • the resin (B) include resins [K1] such as 3,4-epoxycyclohexylmethyl(meth)acrylate/(meth)acrylic acid copolymer and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate/(meth)acrylic acid copolymer; Glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide/tricyclo[5.2.1.0 2,6 ] de
  • Resins [K1] to [K6] may be of one type or of a combination of two or more types.
  • a preferred combination includes, for example, a combination of resins [K2] and [K6].
  • the amount of resin [K2] is, for example, 1 to 50 parts by mass, preferably 5 to 40 parts by mass, and more preferably 10 to 30 parts by mass, per 100 parts by mass of the total of resins [K2] and [K6].
  • the polystyrene-equivalent weight average molecular weight of resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000.
  • the polydispersity of the resin (B) [weight average molecular weight (Mw)/number average molecular weight (Mn)] is preferably 1.1-6, and more preferably 1.2-4.
  • the acid value of resin (B) is preferably 20 to 170 mg-KOH/g, more preferably 25 to 150 mg-KOH/g, and even more preferably 30 to 135 mg-KOH/g, calculated as solid content.
  • the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin (B), and can be determined, for example, by titration with an aqueous potassium hydroxide solution.
  • the content of resin (B) is preferably 2 to 65 mass % relative to the total amount of solids, more preferably 3 to 60 mass %, and even more preferably 5 to 55 mass %.
  • the content of resin (B) is within the above range, a colored pattern can be formed, and the resolution and remaining film rate of the colored pattern tend to improve.
  • the polymerizable compound (C) is a compound that can be polymerized by the active radicals and/or acids generated from the polymerization initiator (D).
  • a compound having a polymerizable ethylenically unsaturated bond can be mentioned.
  • polymerizable compounds having one ethylenically unsaturated bond examples include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the above-mentioned monomers (a), (b), and (c).
  • polymerizable compounds having two ethylenically unsaturated bonds examples include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl)ether of bisphenol A, and 3-methylpentanediol di(meth)acrylate.
  • the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds.
  • examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol poly(meth)acrylate (e.g., pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate), dipentaerythritol poly(meth)acrylate (e.g., dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate), tripentaerythritol poly(meth)acrylate (e.g., tri(meth)acrylate ...
  • the weight average molecular weight of the polymerizable compound (C) is preferably 50 or more and 4,000 or less, more preferably 70 or more and 3,500 or less, even more preferably 100 or more and 3,000 or less, even more preferably 150 or more and 2,900 or less, and particularly preferably 250 or more and 1,500 or less.
  • the content of the polymerizable compound (C) may be, for example, 1% by mass or more and 99% by mass or less, preferably 3% by mass or more and 90% by mass or less, more preferably 5% by mass or more and 80% by mass or less, and even more preferably 7% by mass or more and 70% by mass or less, based on the total amount of solids in the colored curable resin composition.
  • the polymerization initiator (D) may be any compound that can generate active radicals, acids, etc. by the action of light or heat and initiate polymerization.
  • Examples of the polymerization initiator (D) include O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.
  • the O-acyloxime compound is a compound having a partial structure represented by formula (d-1).
  • * represents a bond.
  • O-acyloxime compounds examples include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6- ⁇ 2-methyl-4-(3,3-di N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl
  • IRGACURE OXE01 N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine
  • IRGACURE OXE02 N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine) (both manufactured by BASF)
  • N-1919 manufactured by ADEKA
  • the O-acyloxime compounds include N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine and N-benzoyloxy- At least one selected from the group consisting of 1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine is preferred, with N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1
  • the alkylphenone compound is a compound having a partial structure represented by formula (d-2) or a partial structure represented by formula (d-3).
  • the benzene ring may have a substituent.
  • * represents a bond.
  • Examples of compounds having the partial structure represented by formula (d-2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one.
  • Commercially available products such as Irgacure 369, 907, and 379 (all manufactured by BASF) may also be used.
  • Examples of the compound having a partial structure represented by formula (d-3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, ⁇ , ⁇ -diethoxyacetophenone, and benzyl dimethyl ketal.
  • the alkylphenone compound is preferably a compound having a partial structure represented by formula (d-2).
  • triazine compounds examples include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-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, and 2,4-bis(trichloromethyl)-6- Examples include [2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl
  • the acylphosphine oxide compound may be 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
  • Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may also be used.
  • the biimidazole compound may, for example, be 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxy phenyl) biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl) biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra
  • polymerization initiator (D) examples include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with the polymerization initiator aid (D1) (especially amine), and
  • polymerization initiators that generate acid include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium hexafluoroantimonate, as well as nitrobenzyl tosylates and benzoin tosylates.
  • onium salts such as 4-hydroxyphenyldimethylsulfonium p-
  • a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a biimidazole compound is preferred, a polymerization initiator containing an O-acyloxime compound and/or a biimidazole compound is more preferred, and a polymerization initiator containing an O-acyloxime compound is even more preferred.
  • the content of the polymerization initiator (D) is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C).
  • the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, thereby improving the productivity of the optical filter.
  • the polymerization initiation aid (D1) is a compound used to promote the polymerization of the polymerizable compound (C) whose polymerization has been initiated by the polymerization initiator (D), or a sensitizer. When the polymerization initiation aid (D1) is contained, it is usually used in combination with the polymerization initiator (D).
  • Examples of the polymerization initiator aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.
  • Amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone, with 4,4'-bis(diethylamino)benzophenone being preferred.
  • Commercially available amine compounds such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may also be used.
  • Alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and 2-ethyl-9,10-dibutoxyanthracene.
  • Thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.
  • Carboxylic acid compounds include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.
  • the content is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the total amount of all resins (B) and polymerizable compounds (C) contained in the colored curable resin composition.
  • the solvent (E) is not particularly limited, and any solvent commonly used in the relevant field can be used.
  • the solvent (E) include ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc. Two or more of these solvents may be used in combination. Two or more of these solvents may be used in combination. Two or more of these solvents may be used in combination.
  • Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and gamma-butyrolactone.
  • Ether solvents 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, propylene glycol monoethyl 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 methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and methylanisole.
  • Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate,
  • ether acetates include ethyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate
  • Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.
  • Alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.
  • Aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene, etc.
  • Amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.
  • propylene glycol monomethyl ether acetate propylene glycol monomethyl ether, ethyl lactate and cyclohexanone are preferred, and propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether are more preferred.
  • the content of the solvent (E) is usually 99.99% by mass or less, preferably 40% by mass or more and 99% by mass or less, more preferably 50% by mass or more and 97% by mass or less, even more preferably 70% by mass or more and 96% by mass or less, and even more preferably 73% by mass or more and 95% by mass or less, based on the total amount of the colored curable resin composition.
  • the total amount of solids in the colored curable resin composition is usually 0.01% by mass or more, preferably 1% by mass or more and 60% by mass or less, more preferably 3% by mass or more and 50% by mass or less, even more preferably 4% by mass or more and 30% by mass or less, and even more preferably 5% by mass or more and 27% by mass or less.
  • the content of the solvent (E) is within the above range, the flatness during application is good, and the color density is not insufficient when an optical filter is formed, so that the display characteristics tend to be good.
  • the colored curable resin composition of the present invention may contain a thiol compound (T).
  • the thiol compound (T) is a compound having a sulfanyl group (-SH) in the molecule.
  • Examples of compounds having one sulfanyl group in the molecule include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanylbenzoxazole, 2-sulfanylnicotinic acid, 2-sulfanylpyridine, 2-sulfanylpyridin-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-di
  • Compounds with two or more sulfanyl groups in the molecule include hexanedithiol, decanedithiol, 1,4-bis(methylsulfanyl)benzene, butanediol bis(3-sulfanylpropionate), butanediol bis(3-sulfanyl acetate), ethylene glycol bis(3-sulfanyl acetate), trimethylolpropane tris(3-sulfanyl acetate), butanediol bis(3-sulfanylpropionate), trimethylolpropane tris(3-sulfanyl acetate), Examples include propane tris(3-sulfanylpropionate), trimethylolpropane tris(3-sulfanyl acetate), pentaerythritol tetrakis(3-sulfanylpropionate), pentaerythritol tetrakis(3
  • the content of the thiol compound (T) is preferably 0.5 to 50 parts by mass, more preferably 5 to 45 parts by mass, and even more preferably 10 to 40 parts by mass, per 100 parts by mass of the polymerization initiator (D).
  • the content of the thiol compound (T) is within this range, the sensitivity tends to be high and the developability tends to be good.
  • Leveling Agent (F) examples include silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms, which may have a polymerizable group in the side chain.
  • silicone surfactants include surfactants having a siloxane bond in the molecule.
  • Specific examples include Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (product names: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan, LLC).
  • Fluorosurfactants include surfactants having a fluorocarbon chain in the molecule. Specific examples include Fluorad (registered trademark) FC430 and FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, and RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, EF303, EF351, and EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, and SC105 (manufactured by AGC Corporation), and E5844 (manufactured by Daikin Fine Chemicals Research Institute Ltd.).
  • Fluorad registered trademark
  • FC430 and FC431 manufactured by Sumitomo 3M Limited
  • Megafac registered trademark
  • F142D F171, F172, F17
  • silicone surfactants containing fluorine atoms include surfactants that have siloxane bonds and fluorocarbon chains in the molecule. Specific examples include Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).
  • the content of the leveling agent (F) is preferably 0.0005% by mass or more and 1% by mass or less, more preferably 0.001% by mass or more and 0.5% by mass or less, and even more preferably 0.005% by mass or more and 0.1% by mass or less, based on the total amount of the colored curable resin composition. Note that this content does not include the content of the pigment dispersant. When the content of the leveling agent (F) is within the above range, the flatness of the optical filter can be improved.
  • the colored curable resin composition may contain additives known in the technical field, such as a filler, another polymer compound, an adhesion promoter, a quencher, an antioxidant, a light stabilizer, and a chain transfer agent, as necessary.
  • adhesion promoters examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-sulfur
  • the silane examples include anylpropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethy
  • the colored curable resin composition can be prepared by mixing the colorant (A), the metal compound (G), the resin (B), the polymerizable compound (C), the polymerization initiator (D), and optionally the polymerization initiator aid (D1), the solvent (E), the leveling agent (F), and other components.
  • the mixing can be carried out using known or conventional equipment and conditions.
  • the colorant (A) may be used as a colorant-containing liquid obtained by mixing with a part or all of the solvent (E) in advance and dispersing using a bead mill or the like until the average particle size becomes about 0.2 ⁇ m or less, and it is preferable to use it as a colorant-containing liquid.
  • the dispersant and a part or all of the resin (B) may be blended as necessary.
  • the remaining components are mixed into the colorant-containing liquid obtained in this way to a predetermined concentration, whereby the desired colored curable resin composition can be prepared.
  • the dye when a dye is contained as the colorant (A), the dye may be dissolved in advance in a part or all of the solvent (E) to prepare a solution.
  • the solution is preferably filtered through a filter having a pore size of about 0.01 to 1 ⁇ m.
  • An optical filter can be formed from the colored curable resin composition of the present invention.
  • methods for producing a colored pattern include a photolithography method, an inkjet method, and a printing method.
  • the photolithography method is preferred.
  • the photolithography method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed.
  • a colored coating film which is a cured product of the colored composition layer, can be formed by not using a photomask during exposure and/or not developing.
  • the colored pattern or colored coating film thus formed is the optical filter (color filter) of the present invention.
  • the film thickness of the optical filter (color filter) to be produced is not particularly limited and can be adjusted appropriately depending on the purpose and application, and is, for example, 30 ⁇ m or less, preferably 20 ⁇ m or less, more preferably 6 ⁇ m or less, even more preferably 4.5 ⁇ m or less, and is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, even more preferably 0.3 ⁇ m or more.
  • the substrate may be a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, or soda lime glass with a silica-coated surface; a resin plate such as polycarbonate, polymethylmethacrylate, or polyethylene terephthalate; silicon; or a substrate on which an aluminum, silver, or silver/copper/palladium alloy thin film is formed.
  • a resin plate such as polycarbonate, polymethylmethacrylate, or polyethylene terephthalate
  • silicon or a substrate on which an aluminum, silver, or silver/copper/palladium alloy thin film is formed.
  • another optical filter layer color filter layer
  • a resin layer a resin layer, a transistor, a circuit, or the like
  • a silicon substrate treated with HMDS hexamethyldisilazane
  • each color pixel by photolithography can be carried out using known or conventional equipment and conditions.
  • the pixel can be produced as follows. First, the colored curable resin composition is applied onto a substrate, and then dried by heating and drying (pre-baking) and/or drying under reduced pressure to remove volatile components such as a solvent, thereby obtaining a smooth colored composition layer. Examples of the application method include spin coating, slit coating, and slit and spin coating.
  • the temperature at which the heat drying is performed is preferably 30° C. or higher and 120° C. or lower, and more preferably 50° C. or higher and 110° C. or lower.
  • the heating time is preferably 10 seconds or higher and 60 minutes or lower, and more preferably 30 seconds or higher and 30 minutes or lower.
  • the drying under reduced pressure it is preferable to perform the drying under a pressure of 50 Pa or more and 150 Pa or less at a temperature range of 20° C. or more and 25° C. or less.
  • the thickness of the coloring composition layer is not particularly limited and may be appropriately selected depending on the thickness of the intended optical filter.
  • the colored composition layer is then exposed through a photomask to form the desired colored pattern.
  • a photomask There are no particular limitations on the pattern on the photomask, and a pattern appropriate for the intended use is used.
  • an exposure device such as a mask aligner or stepper, since it is possible to uniformly irradiate the entire exposed surface with parallel light and to accurately align the photomask with the substrate on which the colored composition layer is formed.
  • exposure can be performed without using a photomask.
  • the light source used for exposure is preferably a light source that generates light with a wavelength of 250 nm or more and 450 nm or less.
  • light less than 350 nm may be cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, and 365 nm may be selectively extracted using a bandpass filter that extracts these wavelength ranges.
  • Specific examples include mercury lamps, light-emitting diodes, metal halide lamps, and halogen lamps.
  • the colored composition layer after exposure is brought into contact with a developer and developed to form a colored coating film (colored pattern) on the substrate.
  • the unexposed portion of the colored composition layer is dissolved in the developer and removed by development.
  • the developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide.
  • the concentration of these alkaline compounds in the aqueous solution is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.03% by mass or more and 5% by mass or less.
  • the developer may contain a surfactant.
  • the development method may be any of a paddle method, a dipping method, and a spray method.
  • the substrate may be tilted at any angle during development. After development, the substrate is preferably washed with water.
  • the post-baking temperature is preferably from 80° C. to 250° C., and more preferably from 100° C. to 245° C.
  • the post-baking time is preferably from 1 minute to 120 minutes, and more preferably from 2 minutes to 30 minutes.
  • the colored pattern and colored coating film thus obtained are useful as a color filter.
  • the optical filter is useful as an optical filter (color filter) for use in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.), solid-state imaging devices, and the like.
  • the polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by GPC under the following conditions.
  • Apparatus HLC-8120GPC (manufactured by Tosoh Corporation) Column: TSK-GELG2000HXL Column temperature: 40°C Solvent: tetrahydrofuran Flow rate: 1.0 mL/min Solids concentration of analytical sample: 0.001 to 0.01% by mass Injection volume: 50 ⁇ L Detector: RI
  • Calibration standard material TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
  • the ratio of the weight average molecular weight and the number average molecular weight (Mw/Mn) calculated in terms of polystyrene obtained above was taken as the dispersity.
  • a monomer mixture consisting of 92.4 parts of 2-ethylhexyl acrylate, 184.9 parts of glycidyl methacrylate, and 12.3 parts of dicyclopentanyl methacrylate, to which 35.3 parts of tert-butylperoxy-2-ethylhexanoate (polymerization initiator) had been added, was dropped into the flask from the dropping funnel over 2 hours. After the dropwise addition was completed, the mixture was stirred for another 30 minutes at 120°C to carry out a copolymerization reaction, and an addition copolymer was produced.
  • Example 1 (1) Preparation of Colored Dispersion 1 80.0 parts of compound (II-1), 29.1 parts of dispersant (BYKLPN-6919 manufactured by BYK Corporation) (solid content equivalent), 29.1 parts of resin B-1 (solid content equivalent), 861.8 parts of propylene glycol monomethyl ether acetate, and 1500 parts of 0.2 mm zirconia beads were mixed, and the resulting mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU Corporation). Thereafter, the zirconia beads were removed by filtration to obtain a colored dispersion 1.
  • a paint conditioner manufactured by LAU Corporation
  • Colored curable resin composition 1 was obtained by mixing the following components.
  • the obtained cured film 1 on the glass substrate was measured for absorption spectroscopy before and after the lightfastness test using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation) to determine the absorbance retention rate.
  • the absorbance retention rate in this test is a value obtained by taking the absorbance at the maximum absorption wavelength of the colored coating film 1 before the lightfastness test as 100%. The higher the absorbance retention rate, the better the lightfastness. Furthermore, if the lightfastness of the colored coating film 1 is good, it can be said that the colored pattern produced from the same colored curable resin composition 1 also has good lightfastness.
  • Table 3 The results are shown in Table 3.
  • Example 1 A colored curable resin composition 2 was obtained and a colored coating film 2 was produced in the same manner as in Example 1, except that bis(8-quinolinolato)copper(II) of Example 1 was not used.
  • the composition and light resistance test results of each example are shown in Table 3.

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Abstract

The present invention addresses the problem of providing a coloring curable resin composition capable of maintaining the absorbance of a maximum absorption wavelength.　The present invention relates to a coloring curable resin composition containing a colorant, a resin, a polymerization initiator, a polymerizable compound, and a metal compound, the metal compound containing a compound represented by formula (I). [In formula (I): RA1 to RA6 each independently represent a hydrogen atom, a halogen atom, a C1-20 hydrocarbon group, a hydroxy group, an amino group, a nitro group, a carboxy group, a sulfo group, ORA7, NHRA7, or N(RA7)2, and RA7 represents a C1-10 hydrocarbon group;　XA represents a halogen atom, a C1-20 hydrocarbon group, a hydroxy group, an amino group, a nitro group, a carboxy group, a sulfo group, ORA7, NHRA7, or N(RA7)2; and　MA represents a group 8-13 metal atom where n is an integer of 1-3 and m is an integer of 0 or more, and has a relationship of m = a-n with the atomic value (a) of MA, and the dotted line between MA and N represents a coordinate bond.]

Description

着色硬化性樹脂組成物、光学フィルタ、及び固体撮像素子Colored curable resin composition, optical filter, and solid-state imaging device
　本発明は、着色硬化性樹脂組成物、光学フィルタ、及び固体撮像素子に関するものである。 The present invention relates to a colored curable resin composition, an optical filter, and a solid-state imaging device.
　液晶表示装置、エレクトロルミネッセンス表示装置、及びプラズマディスプレイ等の表示装置やＣＣＤやＣＭＯＳセンサ等の固体撮像素子に使用される光学フィルタは、着色硬化性樹脂組成物から製造される（特許文献１など）。また着色硬化性樹脂組成物に特定の金属化合物を添加することで光を照射した後の色差（ΔＥ＊ab）を抑制できることも知られている（特許文献２～４）。 Optical filters used in displays such as liquid crystal displays, electroluminescent displays, and plasma displays, and solid-state imaging devices such as CCD and CMOS sensors, are manufactured from colored curable resin compositions (see, for example, Patent Document 1). It is also known that the color difference (ΔE* ab ) after irradiation with light can be suppressed by adding a specific metal compound to the colored curable resin composition (Patent Documents 2 to 4).
特開２０１３－１２２５７７号公報JP 2013-122577 A 特開２０１１－１１８３６５号公報JP 2011-118365 A 特開２００４－２９５１１６号公報JP 2004-295116 A 特開２００７－２４９１６０号公報JP 2007-249160 A
　前記着色硬化性樹脂組成物は、光を照射した後の色差（ΔＥ＊ａｂ）が小さいことだけでなく、光を照射した後でも極大吸収波長の吸光度を維持できることも重要である。
　本発明は、極大吸収波長の吸光度を維持できる着色硬化性樹脂組成物を提供することを課題とする。 It is important that the colored curable resin composition not only has a small color difference (ΔE* ab ) after irradiation with light, but also maintains the absorbance at the maximum absorption wavelength even after irradiation with light.
An object of the present invention is to provide a colored curable resin composition capable of maintaining the absorbance at the maximum absorption wavelength.
　本発明に係る要旨は、以下の通りである。
［１］着色剤、樹脂、重合開始剤、重合性化合物、及び金属化合物を含み、前記金属化合物が、式（Ｉ）で表される化合物を含むことを特徴とする着色硬化性樹脂組成物。
Figure JPOXMLDOC01-appb-I000003
［式（Ｉ）中、ＲA1～ＲA6は、互いに独立に、水素原子、ハロゲン原子、炭素数１～２０の炭化水素基、ヒドロキシ基、アミノ基、ニトロ基、カルボキシ基、スルホ基、ＯＲA7、ＮＨＲA7、又はＮ(ＲA7)2を表し、ＲA7は、炭素数１～１０の炭化水素基を表す。
　ＸAは、ハロゲン原子、炭素数１～２０の炭化水素基、ヒドロキシ基、アミノ基、ニトロ基、カルボキシ基、スルホ基、ＯＲA7、ＮＨＲA7、又はＮ(ＲA7)2を表す。
　ＭAは、第８～１３族金属原子を表し、ｎは１～３の整数であり、ｍは、０以上の整数であり、ＭAの原子価ａとの間に、ｍ＝ａ－ｎの関係を有し、ＭA及びＮ間の点線は、配位結合を表す。］
［２］ＭAが第８～１３族の第４周期の金属原子を表す［１］に記載の着色硬化性樹脂組成物。
［３］ＭAが銅原子である［１］又は［２］に記載の着色硬化性樹脂組成物。
［４］着色剤が、式（ＩＩ）で表される化合物を含む［１］～［３］のいずれかに記載の着色硬化性樹脂組成物。
Figure JPOXMLDOC01-appb-I000004
［式（ＩＩ）中、Ｒ1～Ｒ4は、互いに独立に、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又は置換基を有していてもよい炭素数６～２０の１価の芳香族炭化水素基を表し、該飽和炭化水素基に含まれる－ＣＨ2－は、－Ｏ－、－ＣＯ－又は－ＮＲ11－で置き換わっていてもよい。Ｒ1及び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及びＲ4は、一緒になって窒素原子を含む環を形成してもよい。
　Ｒ5は、－ＯＨ、－ＳＯ3 -、－ＳＯ3Ｈ、－ＳＯ3 -Ｚ+、－ＣＯ2Ｈ、－ＣＯ2 -Ｚ+、－ＣＯ2Ｒ8、－ＳＯ3Ｒ8又は－ＳＯ2ＮＲ9Ｒ10を表す。
　Ｒ6及びＲ7は、互いに独立に、水素原子又は炭素数１～６のアルキル基を表す。
　ｍは、０～５の整数を表す。ｍが２以上のとき、複数のＲ5は同一でも異なってもよい。
　ａは、０又は１の整数を表す。
　Ｘは、ハロゲン原子を表す。
　Ｚ+は、+Ｎ（Ｒ11）4、Ｎａ+又はＫ+を表し、４つのＲ11は同一でも異なってもよい。
　Ｒ8は、炭素数１～２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
　Ｒ9及びＲ10は、互いに独立に、水素原子又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、該飽和脂肪族炭化水素基に含まれる－ＣＨ2－は、－Ｏ－、－ＣＯ－、－ＮＨ－又は－ＮＲ8－で置き換っていてもよく、Ｒ9及び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い。
　Ｒ11は、水素原子、炭素数１～２０の１価の飽和炭化水素基又は炭素数７～１０のアラルキル基を表す。］
［５］［１］～［４］のいずれかに記載の着色硬化性樹脂組成物から形成される光学フィルタ。
［６］［５］に記載の光学フィルタを含む固体撮像素子。 The gist of the present invention is as follows.
[1] A colored curable resin composition comprising a colorant, a resin, a polymerization initiator, a polymerizable compound, and a metal compound, wherein the metal compound comprises a compound represented by formula (I).
Figure JPOXMLDOC01-appb-I000003
[In formula (I), R A1 to R A6 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, an amino group, a nitro group, a carboxyl group, a sulfo group, OR A7 , NHR A7 , or N(R A7 ) 2 , where R A7 represents a hydrocarbon group having 1 to 10 carbon atoms.
X A represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, an amino group, a nitro group, a carboxyl group, a sulfo group, OR A7 , NHR A7 , or N(R A7 ) 2 .
M A represents a metal atom of Groups 8 to 13, n is an integer of 1 to 3, m is an integer of 0 or more, and has a relationship of m=a-n with the valence a of M A , and the dotted line between M A and N represents a coordinate bond.
[2] The colored curable resin composition according to [1], wherein M A represents a metal atom of the 4th period of Groups 8 to 13.
[3] The colored curable resin composition according to [1] or [2], wherein M is a copper atom.
[4] The colored curable resin composition according to any one of [1] to [3], wherein the colorant comprises a compound represented by formula (II):
Figure JPOXMLDOC01-appb-I000004
[In formula (II), R 1 to R 4 each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group of 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group of 6 to 20 carbon atoms which may have a substituent, and -CH 2 - contained in the saturated hydrocarbon group may be replaced by -O-, -CO- or -NR 11 -. R 1 and R 2 may be joined together to form a ring containing a nitrogen atom, and R 3 and R 4 may be joined together to form a ring containing a nitrogen atom.]
R5 represents -OH, -SO3- , -SO3H , -SO3 - Z + , -CO2H , -CO2 - Z + , -CO2R8 , -SO3R8 or -SO2NR9R10 .
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 of 0 to 5. When m is 2 or more, multiple R5's may be the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
Z + represents + N(R 11 ) 4 , Na + or K + , and the four R 11 s may be the same or different.
R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R 9 and R 10 each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, in which -CH 2 - contained in the saturated aliphatic hydrocarbon group may be replaced by -O-, -CO-, -NH- or -NR 8 -, and R 9 and R 10 may bond to each other to form a 3- to 10-membered heterocycle containing a nitrogen atom.
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.
[5] An optical filter formed from the colored curable resin composition according to any one of [1] to [4].
[6] A solid-state imaging device comprising the optical filter according to [5].
　本発明によれば、極大吸収波長の吸光度を維持できる光学フィルタを形成可能な着色硬化性樹脂組成物を提供できる。こうした本発明によれば、より長期間に渡って色差（ΔＥ＊ab）を抑制することも可能である。 According to the present invention, it is possible to provide a colored curable resin composition capable of forming an optical filter capable of maintaining the absorbance at the maximum absorption wavelength. According to the present invention, it is also possible to suppress the color difference (ΔE* ab ) for a longer period of time.
　本発明の着色硬化性樹脂組成物は、着色剤（以下、着色剤（Ａ）という場合がある）、樹脂（以下、樹脂（Ｂ）という場合がある）、重合性化合物（以下、重合性化合物（Ｃ）という場合がある）、重合開始剤（以下、重合開始剤（Ｄ）という場合がある）、及び金属化合物（以下、金属化合物（Ｇ）という場合がある）を含み、金属化合物が式（Ｉ）で表される化合物を含む。
　本発明の着色硬化性樹脂組成物は、さらに溶剤（以下、溶剤（Ｅ）という場合がある）を含んでいてもよい。
　本発明の着色硬化性樹脂組成物は、さらに重合開始助剤（以下、重合開始助剤（Ｄ１）という場合がある）を含んでいてもよい。
　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（以下、チオール化合物（Ｔ）という場合がある）を含んでいてもよい。
　本発明の着色硬化性樹脂組成物は、さらにレベリング剤（以下、レベリング剤（Ｆ）という場合がある）を含んでいてもよい。
　なお、本明細書において、各成分として例示する化合物は、特に断りのない限り、単独で又は複数種を組み合わせて使用することができる。 The colored curable resin composition of the present invention contains a colorant (hereinafter, may be referred to as colorant (A)), a resin (hereinafter, may be referred to as resin (B)), a polymerizable compound (hereinafter, may be referred to as polymerizable compound (C)), a polymerization initiator (hereinafter, may be referred to as polymerization initiator (D)), and a metal compound (hereinafter, may be referred to as metal compound (G)), and the metal compound contains a compound represented by formula (I).
The colored curable resin composition of the present invention may further contain a solvent (hereinafter, may be referred to as solvent (E)).
The colored curable resin composition of the present invention may further contain a polymerization initiation aid (hereinafter, may be referred to as polymerization initiation aid (D1)).
The colored curable resin composition of the present invention may further contain a thiol compound (hereinafter, may be referred to as thiol compound (T)).
The colored curable resin composition of the present invention may further contain a leveling agent (hereinafter, may be referred to as leveling agent (F)).
In this specification, the compounds exemplified as each component may be used alone or in combination of two or more kinds, unless otherwise specified.
＜金属化合物（Ｇ）＞
　金属化合物（Ｇ）は、式（Ｉ）で表される化合物を含み、着色剤（好ましくは式（ＩＩ）で表される化合物）と共に使用すると極大吸収波長の吸光度を維持できる。 <Metal compound (G)>
The metal compound (G) includes a compound represented by formula (I), and when used together with a colorant (preferably a compound represented by formula (II)), the absorbance at the maximum absorption wavelength can be maintained.
Figure JPOXMLDOC01-appb-I000005
［式（Ｉ）中、ＲA1～ＲA6は、互いに独立に、水素原子、ハロゲン原子、炭素数１～２０の炭化水素基、ヒドロキシ基、アミノ基、ニトロ基、カルボキシ基、スルホ基、ＯＲA7、ＮＨＲA7、又はＮ(ＲA7)2を表し、ＲA7は、炭素数１～１０の炭化水素基を表す。
　ＸAは、ハロゲン原子、炭素数１～２０の炭化水素基、ヒドロキシ基、アミノ基、ニトロ基、カルボキシ基、スルホ基、ＯＲA7、ＮＨＲA7、又はＮ(ＲA7)2を表す。
　ＭAは、第８～１３族金属原子を表し、ｎは１～３の整数であり、ｍは、０以上の整数であり、ＭAの原子価ａとの間に、ｍ＝ａ－ｎの関係を有し、ＭA及びＮ間の点線は、配位結合を表す。］
Figure JPOXMLDOC01-appb-I000005
[In formula (I), R A1 to R A6 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, an amino group, a nitro group, a carboxyl group, a sulfo group, OR A7 , NHR A7 , or N(R A7 ) 2 , where R A7 represents a hydrocarbon group having 1 to 10 carbon atoms.
X A represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, an amino group, a nitro group, a carboxyl group, a sulfo group, OR A7 , NHR A7 , or N(R A7 ) 2 .
M A represents a metal atom of Groups 8 to 13, n is an integer of 1 to 3, m is an integer of 0 or more, and has a relationship of m=a-n with the valence a of M A , and the dotted line between M A and N represents a coordinate bond.
　ＲA1～ＲA6及びＸAで表されるハロゲン原子としては、塩素原子、フッ素原子、臭素原子、ヨウ素原子等が挙げられる。 Examples of the halogen atom represented by R A1 to R A6 and XA include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.
　ＲA1～ＲA6及びＸAで表される炭素数１～２０の炭素水素基は、脂肪族炭化水素基及び芳香族炭化水素基であってもよく、該脂肪族炭化水素基は、飽和又は不飽和であってもよく、鎖状又は環状（脂環式炭化水素基）であってもよい。 The hydrocarbon groups having 1 to 20 carbon atoms represented by R to R and X may be aliphatic hydrocarbon groups or aromatic hydrocarbon groups, and the aliphatic hydrocarbon groups may be saturated or unsaturated and may be linear or cyclic (alicyclic hydrocarbon groups).
　ＲA1～ＲA6及びＸAで表される飽和又は不飽和鎖状炭化水素基としては、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、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、及びイコシル基等の直鎖状アルキル基；
　イソプロピル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、２－エチルブチル基、３，３－ジメチルブチル基、１，１，３，３－テトラメチルブチル基、１－メチルブチル基、１－エチルプロピル基、３－メチルブチル基、ネオペンチル基、１，１－ジメチルプロピル基、２－メチルペンチル基、３－エチルペンチル基、１，３－ジメチルブチル基、２－プロピルペンチル基、１－エチル－１，２－ジメチルプロピル基、１－メチルペンチル基、４－メチルペンチル基、４－メチルヘキシル基、５－メチルヘキシル基、２－エチルヘキシル基、１－メチルヘキシル基、１－エチルペンチル基、１－プロピルブチル基、３－エチルヘプチル基、２，２－ジメチルヘプチル基、１－メチルヘプチル基、１－エチルヘキシル基、１－プロピルペンチル基、１－メチルオクチル基、１－エチルヘプチル基、１－プロピルヘキシル基、１－ブチルペンチル基、１－メチルノニル基、１－エチルオクチル基、１－プロピルヘプチル基及び１－ブチルヘキシル基等の分枝鎖状アルキル基；
　エテニル基（ビニル基）、プロペニル基（例えば、１－プロペニル基、２－プロペニル基（アリル基））、１－メチルエテニル基、ブテニル基（例えば、１－ブテニル基、２－ブテニル基、３－ブテニル基）、３－メチル－１－ブテニル基、１－メチル－１－ブテニル基、３－メチル－２－ブテニル基、１，３－ブタジエニル基、３－メチル－１，２－ブタジエニル基、１－（２－プロペニル）エテニル基、１－（１－メチルエテニル）エテニル基、１，１－ジメチル－２－プロペニル基、１，２－ジメチル－１－プロペニル基、１－エチル－２－プロペニル基、ペンテニル基（例えば、１－ペンテニル基、２－ペンテニル基、３－ペンテニル基、４－ペンテニル基）、１－（１，１－ジメチルエチル）エテニル基、１，３－ジメチル－１－ブテニル基、ヘキセニル基（例えば、１－ヘキセニル基、５－ヘキセニル基）、ヘプテニル基（例えば、１－ヘプテニル基、６－ヘプテニル基）、オクテニル基（例えば、１－オクテニル基、７－オクテニル基）、ノネニル基（例えば、１－ノネニル基、８－ノネニル基）、デセニル基（例えば、１－デセニル基、９－デセニル基）、ウンデセニル基、ドデセニル基、トリデセニル基、テトラデセニル基、ペンタデセニル基、ヘキサデセニル基、ヘプタデセニル基、オクタデセニル基、ノナデセニル基、イコセニル基等のアルケニル基；
　エチニル基、プロピニル基（例えば、１－プロピニル基、２－プロピニル基）、ブチニル基（例えば、１－ブチニル基、２－ブチニル基、３－ブチニル基）、ペンチニル基（例えば、２－ペンチニル基、３－ペンチニル基、４－ペンチニル基）、１－メチル－３－ブチニル基、１，１－ジメチル－２－プロピニル基、ヘキシニル基（例えば、２－ヘキシニル基、５－ヘキシニル基）、１－エチル－３－ブチニル基、ヘプチニル基（例えば、２－ヘプチニル基、６－ヘプチニル基）、１－エチル－３－ペンチニル基、オクチニル基（例えば、１－オクチニル基、２－オクチニル基、７－オクチニル基）、ノニニル基（例えば、２－ノニニル基、８－ノニニル基）、デシニル基（例えば、２－デシニル基、９－デシニル基）、ウンデシニル基、ドデシニル基、トリデシニル基、テトラデシニル基、ペンタデシニル基、ヘキサデシニル基、ヘプタデシニル基、オクタデシニル基、ノナデシニル基及びイコシニル基等のアルキニル基；
等が挙げられる。 Examples of the saturated or unsaturated chain hydrocarbon group represented by R A1 to R A6 and X A include straight-chain alkyl groups such as 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, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an icosyl group;
Isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylbutyl group, 3,3-dimethylbutyl group, 1,1,3,3-tetramethylbutyl group, 1-methylbutyl group, 1-ethylpropyl group, 3-methylbutyl group, neopentyl group, 1,1-dimethylpropyl group, 2-methylpentyl group, 3-ethylpentyl group, 1,3-dimethylbutyl group, 2-propylpentyl group, 1-ethyl-1,2-dimethylpropyl group, 1-methylpentyl group, 4-methylpentyl group, 4-methyl branched alkyl groups such as 2-ethylhexyl, 5-methylhexyl, 2-ethylhexyl, 1-methylhexyl, 1-ethylpentyl, 1-propylbutyl, 3-ethylheptyl, 2,2-dimethylheptyl, 1-methylheptyl, 1-ethylhexyl, 1-propylpentyl, 1-methyloctyl, 1-ethylheptyl, 1-propylhexyl, 1-butylpentyl, 1-methylnonyl, 1-ethyloctyl, 1-propylheptyl, and 1-butylhexyl groups;
Ethenyl group (vinyl group), propenyl group (for example, 1-propenyl group, 2-propenyl group (allyl group)), 1-methylethenyl group, butenyl group (for example, 1-butenyl group, 2-butenyl group, 3-butenyl group), 3-methyl-1-butenyl group, 1-methyl-1-butenyl group, 3-methyl-2-butenyl group, 1,3-butadienyl group, 3-methyl-1,2-butadienyl group, 1-(2-propenyl)ethenyl group, 1-(1-methylethenyl)ethenyl group, 1,1-dimethyl-2-propenyl group, 1,2-dimethyl-1-propenyl group, 1-ethyl-2-propenyl group, pentenyl group (for example, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, alkenyl groups such as 1-(1,1-dimethylethyl)ethenyl group, 1,3-dimethyl-1-butenyl group, hexenyl group (e.g., 1-hexenyl group, 5-hexenyl group), heptenyl group (e.g., 1-heptenyl group, 6-heptenyl group), octenyl group (e.g., 1-octenyl group, 7-octenyl group), nonenyl group (e.g., 1-nonenyl group, 8-nonenyl group), decenyl group (e.g., 1-decenyl group, 9-decenyl group), undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, and icosenyl group;
Ethynyl group, propynyl group (e.g., 1-propynyl group, 2-propynyl group), butynyl group (e.g., 1-butynyl group, 2-butynyl group, 3-butynyl group), pentynyl group (e.g., 2-pentynyl group, 3-pentynyl group, 4-pentynyl group), 1-methyl-3-butynyl group, 1,1-dimethyl-2-propynyl group, hexynyl group (e.g., 2-hexynyl group, 5-hexynyl group), 1-ethyl-3-butynyl group, heptynyl group (e.g., 2-heptynyl group, 6- alkynyl groups such as a 1-octynyl group, a 2-octynyl group, a 7-octynyl group, a nonynyl group (for example, a 2-nonynyl group, an 8-nonynyl group), a decynyl group (for example, a 2-decynyl group, a 9-decynyl group), an undecynyl group, a dodecynyl group, a tridecynyl group, a tetradecynyl group, a pentadecynyl group, a hexadecinyl group, a heptadecynyl group, an octadecynyl group, a nonadecinyl group, and an icosinyl group;
etc.
　ＲA1～ＲA6及びＸAで表される飽和鎖状炭化水素基（すなわち、直鎖状アルキル基、分枝鎖状アルキル基）の炭素数は、好ましくは１～１０であり、より好ましくは１～７であり、さらに好ましくは１～５である。
　ＲA1～ＲA6及びＸAで表される不飽和鎖状炭化水素基（すなわち、アルケニル基、アルキニル基）の炭素数は、好ましくは２～１０であり、より好ましくは２～７であり、さらに好ましくは２～５である。 The number of carbon atoms in the saturated chain hydrocarbon group (i.e., linear alkyl group, branched alkyl group) represented by R A1 to R A6 and XA is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 5.
The unsaturated chain hydrocarbon groups (that is, alkenyl groups, alkynyl groups) represented by R A1 to R A6 and X A preferably have 2-10 carbon atoms, more preferably 2-7 carbon atoms, and even more preferably 2-5 carbon atoms.
　ＲA1～ＲA6及びＸAで表される飽和又は不飽和脂環式炭化水素基としては、シクロプロピル基、１－メチルシクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、１－メチルシクロヘキシル基、２－メチルシクロヘキシル基、３－メチルシクロヘキシル基、４－メチルシクロヘキシル基、１，２－ジメチルシクロヘキシル基、１，３－ジメチルシクロヘキシル基、１，４－ジメチルシクロヘキシル基、２，３－ジメチルシクロヘキシル基、２，４－ジメチルシクロヘキシル基、２，５－ジメチルシクロヘキシル基、２，６－ジメチルシクロヘキシル基、３，４－ジメチルシクロヘキシル基、３，５－ジメチルシクロヘキシル基、２，２－ジメチルシクロヘキシル基、３，３－ジメチルシクロヘキシル基、４，４－ジメチルシクロヘキシル基、シクロオクチル基、２，４，６－トリメチルシクロヘキシル基、２，２，６，６－テトラメチルシクロヘキシル基、３，３，５，５－テトラメチルシクロヘキシル基、４－ペンチルシクロヘキシル基、４－オクチルシクロヘキシル基及び４－シクロヘキシルシクロヘキシル基等のシクロアルキル基；
　シクロヘキセニル基（例えば、シクロヘキサ－１－エン－１－イル基、シクロヘキサ－２－エン－１－イル基、シクロヘキサ－３－エン－１－イル基）、シクロヘプテニル基及びシクロオクテニル基等のシクロアルケニル基；
　ノルボルニル基、ノルボルネニル基、アダマンチル基及びビシクロ［２．２．２］オクチル基等の飽和又は不飽和多環式炭化水素基；
等が挙げられる。
　ＲA1～ＲA6及びＸAで表される飽和又は不飽和脂環式炭化水素基の炭素数は、好ましくは３～１０であり、より好ましくは３～７である。 Examples of the saturated or unsaturated alicyclic hydrocarbon group represented by R A1 to R A6 and XA include a cyclopropyl group, a 1-methylcyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a 1-methylcyclohexyl group, a 2-methylcyclohexyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, a 1,2-dimethylcyclohexyl group, a 1,3-dimethylcyclohexyl group, a 1,4-dimethylcyclohexyl group, a 2,3-dimethylcyclohexyl group, a 2,4-dimethylcyclohexyl group, a 2,5-dimethylcyclohexyl group, a 2,6-dimethylcyclohexyl group, a 2,7-dimethylcyclohexyl group, a 2,8-dimethylcyclohexyl group, a 2,9-dimethylcyclohexyl group, a 2,10-dimethylcyclohexyl group, a 2,11-dimethylcyclohexyl group, a 2,12-dimethylcyclohexyl group, a 2,13-dimethylcyclohexyl group, a 2,14-dimethylcyclohexyl group, a 2,21-dimethylcyclohexyl group, a 2,32-dimethylcyclohexyl group, a 2,42-dimethylcyclohexyl group, a 2,53-dimethylcyclohexyl group, a 2,22-dimethylcyclohexyl group, a 2,34-dimethylcyclohexyl group, a 2,46-dimethylcyclohexyl group, a 2,55-dimethylcyclohexyl group, a 2,236-dimethylcyclohexyl group, a 2,246-dimethylcyclohexyl group, a 2,256-dimethylcyclohexyl group, a 2,266-dimethylcyclohexyl group, a 2,276-dimethylcyclohexyl group, a 2,286-dimethylcyclohexyl group, a 2,296-dimethylcyclohexyl group, a 2,35-dimethylcyclohexyl group, a cycloalkyl groups such as a 2,6-dimethylcyclohexyl group, a 3,4-dimethylcyclohexyl group, a 3,5-dimethylcyclohexyl group, a 2,2-dimethylcyclohexyl group, a 3,3-dimethylcyclohexyl group, a 4,4-dimethylcyclohexyl group, a cyclooctyl group, a 2,4,6-trimethylcyclohexyl group, a 2,2,6,6-tetramethylcyclohexyl group, a 3,3,5,5-tetramethylcyclohexyl group, a 4-pentylcyclohexyl group, a 4-octylcyclohexyl group, and a 4-cyclohexylcyclohexyl group;
cycloalkenyl groups such as a cyclohexenyl group (for example, a cyclohex-1-en-1-yl group, a cyclohex-2-en-1-yl group, a cyclohex-3-en-1-yl group), a cycloheptenyl group, and a cyclooctenyl group;
Saturated or unsaturated polycyclic hydrocarbon groups such as a norbornyl group, a norbornenyl group, an adamantyl group, and a bicyclo[2.2.2]octyl group;
etc.
The saturated or unsaturated alicyclic hydrocarbon group represented by R A1 to R A6 and XA preferably has 3 to 10 carbon atoms, and more preferably 3 to 7 carbon atoms.
　ＲA1～ＲA6及びＸAで表される芳香族炭化水素基としては、フェニル基、ｏ－トリル基、ｍ－トリル基、ｐ－トリル基、２－エチルフェニル基、３－エチルフェニル基、４－エチルフェニル基、２，３－ジメチルフェニル基、２，４－ジメチルフェニル基、２，５－ジメチルフェニル基、２，６－ジメチルフェニル基、３，４－ジメチルフェニル基、３，５－ジメチルフェニル基、４－ビニルフェニル基、ｏ－イソプロピルフェニル基、ｍ－イソプロピルフェニル基、ｐ－イソプロピルフェニル基、ｏ－ｔｅｒｔ－ブチルフェニル基、ｍ－ｔｅｒｔ－ブチルフェニル基、ｐ－ｔｅｒｔ－ブチルフェニル基、３，５－ジ（ｔｅｒｔ－ブチル）フェニル基、３，５－ジ（ｔｅｒｔ－ブチル）－４－メチルフェニル基、４－ブチルフェニル基、４－ペンチルフェニル基、２，６－ビス（１－メチルエチル）フェニル基、２，４，６－トリス（１－メチルエチル）フェニル基、４－シクロヘキシルフェニル基、２，４，６－トリメチルフェニル基、４－オクチルフェニル基、４－（１，１，３，３－テトラメチルブチル）フェニル基、１－ナフチル基、２－ナフチル基、６－メチル－２－ナフチル基、５，６，７，８－テトラヒドロ－１－ナフチル基、５，６，７，８－テトラヒドロ－２－ナフチル基、フルオレニル基、フェナントリル基、アントリル基、２－ドデシルフェニル基、３－ドデシルフェニル基、４－ドデシルフェニル基、ペリレニル基、クリセニル基及びピレニル基等の芳香族炭化水素基；等が挙げられる。
　ＲA1～ＲA6及びＸAで表される芳香族炭化水素基の炭素数は、好ましくは６～２０であり、より好ましくは６～１０であり、さらに好ましくは６～８である。 Examples of the aromatic hydrocarbon group represented by R A1 to R A6 and XA include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2-ethylphenyl group, a 3-ethylphenyl group, a 4-ethylphenyl group, a 2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,6-dimethylphenyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 4-vinylphenyl group, an o-isopropylphenyl group, an m-isopropylphenyl group, a p-isopropylphenyl group, an o-tert-butylphenyl group, an m-tert-butylphenyl group, a p-tert-butylphenyl group, a 3,5-di(tert-butyl)phenyl group, a 3,5-di(tert-butyl)-4-methylphenyl group, a 4- aromatic hydrocarbon groups such as a butylphenyl group, a 4-pentylphenyl group, a 2,6-bis(1-methylethyl)phenyl group, a 2,4,6-tris(1-methylethyl)phenyl group, a 4-cyclohexylphenyl group, a 2,4,6-trimethylphenyl group, a 4-octylphenyl group, a 4-(1,1,3,3-tetramethylbutyl)phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 6-methyl-2-naphthyl group, a 5,6,7,8-tetrahydro-1-naphthyl group, a 5,6,7,8-tetrahydro-2-naphthyl group, a fluorenyl group, a phenanthryl group, an anthryl group, a 2-dodecylphenyl group, a 3-dodecylphenyl group, a 4-dodecylphenyl group, a perylenyl group, a chrysenyl group, and a pyrenyl group; and the like.
The aromatic hydrocarbon groups represented by R A1 to R A6 and XA preferably have 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, and even more preferably 6 to 8 carbon atoms.
　ＲA1～ＲA6及びＸAで表される炭化水素基は、上記に挙げた炭化水素基（例えば芳香族炭化水素基と、鎖状炭化水素基及び脂環式炭化水素基の少なくとも１つ）を組合せた基であってもよく、
　ベンジル基、（２－メチルフェニル）メチル基、（３－メチルフェニル）メチル基、（４－メチルフェニル）メチル基、（２－エチルフェニル）メチル基、（３－エチルフェニル）メチル基、（４－エチルフェニル）メチル基、（２－（ｔｅｒｔ－ブチル）フェニル）メチル基、（３－（ｔｅｒｔ－ブチル）フェニル）メチル基、（４－（ｔｅｒｔ－ブチル）フェニル）メチル基、（３，５－ジメチルフェニル）メチル基、１－フェニルエチル基、１－メチル－１－フェニルエチル基、１，１－ジフェニルエチル基、（１－ナフチル）メチル基及び（２－ナフチル）メチル基等のアラルキル基；
　１－フェニルエテニル基、２－フェニルエテニル基（フェニルビニル基）、２，２－ジフェニルエテニル基、２－フェニル－２－（１－ナフチル）エテニル基等のアリールアルケニル基；
　フェニルエチニル基、３－フェニル－２－プロピニル基等のアリールアルキニル基；
　ビフェニリル基、ターフェニリル基等の１つ以上のフェニル基が結合したフェニル基；
　シクロヘキシルメチルフェニル基、ベンジルフェニル基、（ジメチル（フェニル）メチル）フェニル基等が挙げられる。
　これらの炭素数は、好ましくは７～１８であり、より好ましくは７～１５である。 The hydrocarbon groups represented by R to R and X may be a group obtained by combining the above-mentioned hydrocarbon groups (for example, an aromatic hydrocarbon group and at least one of a chain hydrocarbon group and an alicyclic hydrocarbon group),
aralkyl groups such as a benzyl group, a (2-methylphenyl)methyl group, a (3-methylphenyl)methyl group, a (4-methylphenyl)methyl group, a (2-ethylphenyl)methyl group, a (3-ethylphenyl)methyl group, a (4-ethylphenyl)methyl group, a (2-(tert-butyl)phenyl)methyl group, a (3-(tert-butyl)phenyl)methyl group, a (4-(tert-butyl)phenyl)methyl group, a (3,5-dimethylphenyl)methyl group, a 1-phenylethyl group, a 1-methyl-1-phenylethyl group, a 1,1-diphenylethyl group, a (1-naphthyl)methyl group and a (2-naphthyl)methyl group;
Arylalkenyl groups such as a 1-phenylethenyl group, a 2-phenylethenyl group (a phenylvinyl group), a 2,2-diphenylethenyl group, and a 2-phenyl-2-(1-naphthyl)ethenyl group;
Arylalkynyl groups such as a phenylethynyl group, a 3-phenyl-2-propynyl group, etc.;
A phenyl group having one or more phenyl groups bonded thereto, such as a biphenylyl group or a terphenylyl group;
Examples thereof include a cyclohexylmethylphenyl group, a benzylphenyl group, and a (dimethyl(phenyl)methyl)phenyl group.
These preferably have 7 to 18 carbon atoms, and more preferably 7 to 15 carbon atoms.
　ＲA1～ＲA6及びＸAで表される基は、上記に挙げた炭化水素基（例えば鎖状炭化水素基と脂環式炭化水素基）を組合せた基として、例えば、シクロプロピルメチル基、シクロプロピルエチル基、シクロブチルメチル基、シクロブチルエチル基、シクロペンチルメチル基、シクロペンチルエチル基、シクロヘキシルメチル基、（２－メチルシクロヘキシル）メチル基、シクロヘキシルエチル基、アダマンチルメチル基等の１つ以上の脂環式炭化水素基が結合したアルキル基であってもよい。
　これらの炭素数は、好ましくは４～１５であり、より好ましくは４～１０である。 The groups represented by R to R and X may be groups combining the above-listed hydrocarbon groups (for example, a chain hydrocarbon group and an alicyclic hydrocarbon group), such as an alkyl group having one or more alicyclic hydrocarbon groups bonded thereto, such as a cyclopropylmethyl group, a cyclopropylethyl group, a cyclobutylmethyl group, a cyclobutylethyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, a (2-methylcyclohexyl)methyl group, a cyclohexylethyl group, or an adamantylmethyl group.
These preferably have 4 to 15 carbon atoms, and more preferably 4 to 10 carbon atoms.
　ＲA7で表される炭素水素基としては、ＲA1～ＲA6及びＸAで表される炭素数１～２０の炭素水素基のうち炭素数１～１０と同様なものが挙げられる。 Examples of the hydrocarbon group represented by R A7 include the same ones having 1 to 10 carbon atoms among the hydrocarbon groups having 1 to 20 carbon atoms represented by R A1 to R A6 and XA .
　ＲA1～ＲA6及びＸAで表されるＯＲA7として、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、ノニルオキシ基、デシルオキシ等が挙げられる。 Examples of OR A7 represented by R A1 to R A6 and XA 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, a nonyloxy group, and a decyloxy group.
　ＲA1～ＲA6及びＸAで表されるＮＨＲA7として、Ｎ－メチルアミノ基、Ｎ－エチルアミノ基、Ｎ－プロピルアミノ基、Ｎ－イソプロピルアミノ基、Ｎ－ブチルアミノ基、Ｎ－イソブチルアミノ基、Ｎ－ｓｅｃ－ブチルアミノ基、Ｎ－ｔｅｒｔ－ブチルアミノ基、Ｎ－ペンチルアミノ基、Ｎ－（１－エチルプロピル）アミノ基、Ｎ－ヘキシルアミノ基、Ｎ－（２－エチル）ヘキシルアミノ基、Ｎ－ヘプチルアミノ基、Ｎ－オクチルアミノ基、Ｎ－ノニルアミノ基、Ｎ－フェニルアミノ基、Ｎ－デシルアミノ基等が挙げられる。 Examples of NHR represented by R to R and XA include an N-methylamino group, an N-ethylamino group, an N-propylamino group, an N-isopropylamino group, an N-butylamino group, an N-isobutylamino group, an N-sec-butylamino group, an N-tert-butylamino group, an N-pentylamino group, an N-(1-ethylpropyl)amino group, an N-hexylamino group, an N-(2-ethyl)hexylamino group, an N-heptylamino group, an N-octylamino group, an N-nonylamino group, an N-phenylamino group, and an N-decylamino group.
　ＲA1～ＲA6及びＸAで表されるＮ（ＲA7）2として、Ｎ，Ｎ－ジメチルアミノ基、Ｎ，Ｎ－ジエチルアミノ基、Ｎ，Ｎ－ジプロピルアミノ基、Ｎ，Ｎ－ジイソプロピルアミノ基、Ｎ，Ｎ－ジブチルアミノ基、Ｎ，Ｎ－ジイソブチルアミノ基、Ｎ，Ｎ－ジｓｅｃ－ブチルアミノ基、Ｎ，Ｎ－ジｔｅｒｔ－ブチルアミノ基、Ｎ，Ｎ－ジペンチルアミノ基、Ｎ，Ｎ－ジ（１－エチルプロピル）アミノ基、Ｎ，Ｎ－ジヘキシルアミノ基、Ｎ，Ｎ－ジ（２－エチル）ヘキシルアミノ基、Ｎ，Ｎ－ジヘプチルアミノ基、Ｎ，Ｎ－ジフェニルアミノ基、Ｎ，Ｎ－ジオクチルアミノ基、Ｎ，Ｎ－ジノニルアミノ基、Ｎ，Ｎ－エチルメチルアミノ基、Ｎ，Ｎ－プロピルメチルアミノ基、Ｎ，Ｎ－イソプロピルメチルアミノ基、Ｎ，Ｎ－ブチルメチルアミノ基、Ｎ，Ｎ－デシルメチルアミノ基、Ｎ，Ｎ－ｔｅｒｔ－ブチルメチルアミノ基、Ｎ，Ｎ－フェニルメチルアミノ基等が挙げられる。 N(R A7 ) 2 represented by R A1 to R A6 and XA includes an N,N-dimethylamino group, an N,N-diethylamino group, an N,N-dipropylamino group, an N,N-diisopropylamino group, an N,N-dibutylamino group, an N,N-diisobutylamino group, an N,N-disec-butylamino group, an N,N-ditert-butylamino group, an N,N-dipentylamino group, an N,N-di(1-ethylpropyl)amino group, an N,N-dihexylamino group, an N,N-di(2-ethyl) Examples of such an amino group include a hexylamino group, an N,N-diheptylamino group, an N,N-diphenylamino group, an N,N-dioctylamino group, an N,N-dinonylamino group, an N,N-ethylmethylamino group, an N,N-propylmethylamino group, an N,N-isopropylmethylamino group, an N,N-butylmethylamino group, an N,N-decylmethylamino group, an N,N-tert-butylmethylamino group, and an N,N-phenylmethylamino group.
　ＭAは、第８～１３族金属原子である。
　ＭAで表される第８～１３族金属原子としては、鉄（第４周期）、ルテニウム（第５周期）、オスミウム（第６周期）等の第８族、コバルト（第４周期）、ロジウム（第５周期）、イリジウム（第６周期）等の第９族、ニッケル（第４周期）、パラジウム（第５周期）、白金（第６周期）等の第１０族、銅（第４周期）、銀（第５周期）、金（第６周期）
等の第１１族、亜鉛（第４周期）、カドミウム（第５周期）、水銀（第６周期）等の第１２族、アルミニウム（第３周期）、ガリウム（第４周期）、インジウム（第５周期）、タリウム（第６周期）等の第１３族等が挙げられる。 M A is a Group 8 to 13 metal atom.
Examples of metal atoms of Groups 8 to 13 represented by M A include Group 8 elements such as iron (Period 4), ruthenium (Period 5), and osmium (Period 6), Group 9 elements such as cobalt (Period 4), rhodium (Period 5), and iridium (Period 6), Group 10 elements such as nickel (Period 4), palladium (Period 5), and platinum (Period 6), and Group 10 elements such as copper (Period 4), silver (Period 5), and gold (Period 6).
Group 11 elements such as zinc (4th period), cadmium (5th period), and mercury (6th period); Group 12 elements such as aluminum (3rd period), gallium (4th period), indium (5th period), and thallium (6th period); and Group 13 elements such as aluminum (3rd period), gallium (4th period), indium (5th period), and thallium (6th period).
　ＭAは、好ましくは第８～１３族の第４～５周期の金属原子、さらに好ましくは第８～１３族の第４周期の金属原子、さらにより好ましくは銅原子である。 M A is preferably a metal atom of periods 4 to 5 in groups 8 to 13, more preferably a metal atom of periods 4 in groups 8 to 13, and even more preferably a copper atom.
　ｎは１～３の整数であり、好ましくは２又は３、より好ましくは２である。 n is an integer from 1 to 3, preferably 2 or 3, and more preferably 2.
　ｍは、０以上の整数であり、好ましくは０以上１０以下の整数、より好ましくは０以上５以下の整数、さらに好ましくは０以上３以下の整数、さらにより好ましくは０以上１以下の整数、特に好ましくは０である。 m is an integer of 0 or more, preferably an integer of 0 or more and 10 or less, more preferably an integer of 0 or more and 5 or less, even more preferably an integer of 0 or more and 3 or less, even more preferably an integer of 0 or more and 1 or less, and particularly preferably 0.
　ＲA1～ＲA6は、互いに独立に、水素原子、ハロゲン原子、炭素数１～２０の炭化水素基を表すことが好ましく、水素原子、ハロゲン原子、炭素数１～１５の脂肪族炭化水素基又は炭素数６～１５の芳香族炭化水素基を表すことがより好ましく、水素原子、ハロゲン原子、炭素数１～１０の脂肪族炭化水素基又は炭素数６～１０の芳香族炭化水素基を表すことがさらに好ましく、水素原子、炭素数１～５の脂肪族炭化水素基又は炭素数６～１０の芳香族炭化水素基を表すことがさらにより好ましく、水素原子であることが特に好ましい。
　ｍは０であることが好ましいが、１以上であってもよい。ｍが１以上のとき、ＸAは、ハロゲン原子、ヒドロキシ基、アミノ基、又はＮ(ＲA7)2を表すことが好ましい。 R A1 to R A6 each independently preferably represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 15 carbon atoms, even more preferably a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, even more preferably a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and particularly preferably a hydrogen atom.
m is preferably 0, but may be equal to or greater than 1. When m is equal to or greater than 1, X A preferably represents a halogen atom, a hydroxy group, an amino group, or N(R A7 ) 2 .
　式（Ｉ）で表される化合物としては、式（Ｉ－Ａ１）～式（Ｉ－Ａ８０）で表される化合物が挙げられ、好ましくは式（Ｉ－Ａ１）～式（Ｉ－Ａ６０）で表される化合物であり、より好ましくは式（Ｉ－Ａ１）～式（Ｉ－Ａ１０）で表される化合物である。 The compounds represented by formula (I) include compounds represented by formulas (I-A1) to (I-A80), preferably compounds represented by formulas (I-A1) to (I-A60), and more preferably compounds represented by formulas (I-A1) to (I-A10).
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　式（Ｉ）で表される化合物の含有率は、金属化合物１００質量％中、好ましくは７０質量％以上、より好ましくは８０質量％以上、さらに好ましくは９０質量％以上、さらにより好ましくは１００質量％である。 The content of the compound represented by formula (I) is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 100% by mass, based on 100% by mass of the metal compound.
　金属化合物の含有量は、着色剤１００質量部に対し、好ましくは０．１～７５質量部、より好ましくは１～５０質量部、さらに好ましくは２～４０質量部、さらにより好ましくは３～３０質量部である。 The content of the metal compound is preferably 0.1 to 75 parts by mass, more preferably 1 to 50 parts by mass, even more preferably 2 to 40 parts by mass, and even more preferably 3 to 30 parts by mass, per 100 parts by mass of the colorant.
　金属化合物の含有率は、着色硬化性樹脂組成物の固形分１００質量％中、好ましくは０．１～３０質量％、より好ましくは０．５～２０質量％、さらに好ましくは１～１５質量％、さらにより好ましくは２～１０質量％である。 The content of the metal compound is preferably 0.1 to 30 mass%, more preferably 0.5 to 20 mass%, even more preferably 1 to 15 mass%, and even more preferably 2 to 10 mass%, based on 100 mass% of the solid content of the colored curable resin composition.
＜着色剤（Ａ）＞
　着色剤（Ａ）は、式（ＩＩ）で表される化合物を含むことが好ましい。式（ＩＩ）で表される化合物に大気中で光を照射して極大吸収波長の吸光度が下がる場合があっても、式（ＩＩ）で表される化合物と本発明で特定する金属化合物とを組み合わせると、吸光度の低下を抑制できる。
Figure JPOXMLDOC01-appb-I000008
［式（ＩＩ）中、Ｒ1～Ｒ4は、互いに独立に、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又は置換基を有していてもよい炭素数６～２０の１価の芳香族炭化水素基を表し、該飽和炭化水素基に含まれる－ＣＨ2－は、－Ｏ－、－ＣＯ－又は－ＮＲ11－で置き換わっていてもよい。Ｒ1及び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及びＲ4は、一緒になって窒素原子を含む環を形成してもよい。
　Ｒ5は、－ＯＨ、－ＳＯ3 -、－ＳＯ3Ｈ、－ＳＯ3 -Ｚ+、－ＣＯ2Ｈ、－ＣＯ2 -Ｚ+、－ＣＯ2Ｒ8、－ＳＯ3Ｒ8又は－ＳＯ2ＮＲ9Ｒ10を表す。
　Ｒ6及びＲ7は、互いに独立に、水素原子又は炭素数１～６のアルキル基を表す。
　ｍは、０～５の整数を表す。ｍが２以上のとき、複数のＲ5は同一でも異なってもよい。
　ａは、０又は１の整数を表す。
　Ｘは、ハロゲン原子を表す。
　Ｚ+は、+Ｎ（Ｒ11）4、Ｎａ+又はＫ+を表し、４つのＲ11は同一でも異なってもよい。
　Ｒ8は、炭素数１～２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
　Ｒ9及びＲ10は、互いに独立に、水素原子又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、該飽和脂肪族炭化水素基に含まれる－ＣＨ2－は、－Ｏ－、－ＣＯ－、－ＮＨ－又は－ＮＲ8－で置き換っていてもよく、Ｒ9及び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い。
　Ｒ11は、水素原子、炭素数１～２０の１価の飽和炭化水素基又は炭素数７～１０のアラルキル基を表す。］ <Colorant (A)>
The colorant (A) preferably contains a compound represented by formula (II). Even if the absorbance at the maximum absorption wavelength decreases when the compound represented by formula (II) is irradiated with light in the atmosphere, the decrease in absorbance can be suppressed by combining the compound represented by formula (II) with the metal compound specified in the present invention.
Figure JPOXMLDOC01-appb-I000008
[In formula (II), R 1 to R 4 each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group of 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group of 6 to 20 carbon atoms which may have a substituent, and -CH 2 - contained in the saturated hydrocarbon group may be replaced by -O-, -CO- or -NR 11 -. R 1 and R 2 may be joined together to form a ring containing a nitrogen atom, and R 3 and R 4 may be joined together to form a ring containing a nitrogen atom.]
R5 represents -OH, -SO3- , -SO3H , -SO3 - Z + , -CO2H , -CO2 - Z + , -CO2R8 , -SO3R8 or -SO2NR9R10 .
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 of 0 to 5. When m is 2 or more, multiple R5's may be the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
Z + represents + N(R 11 ) 4 , Na + or K + , and the four R 11 s may be the same or different.
R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R 9 and R 10 each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, in which -CH 2 - contained in the saturated aliphatic hydrocarbon group may be replaced by -O-, -CO-, -NH- or -NR 8 -, and R 9 and R 10 may bond to each other to form a 3- to 10-membered heterocycle containing a nitrogen atom.
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.
　Ｒ１～Ｒ4及びＲ8～Ｒ11で表される炭素数１～２０の１価の飽和炭化水素基としては、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、イコシル基等の直鎖状アルキル基；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分岐鎖状アルキル基；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。 Examples of the monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms represented by R 1 to R 4 and R 8 to R 11 include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and icosyl groups; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl groups; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl groups.
　Ｒ1～Ｒ4で表される炭素数６～２０の１価の芳香族炭化水素基としては、例えば、フェニル基、ｏ－トリル基、ｍ－トリル基、ｐ－トリル基、２－エチルフェニル基、３－エチルフェニル基、４－エチルフェニル基、２，３－ジメチルフェニル基、２，４－ジメチルフェニル基、２，５－ジメチルフェニル基、２，６－ジメチルフェニル基、３，４－ジメチルフェニル基、３，５－ジメチルフェニル基、４－ビニルフェニル基、ｏ－イソプロピルフェニル基、ｍ－イソプロピルフェニル基、ｐ－イソプロピルフェニル基、ｏ－ｔｅｒｔ－ブチルフェニル基、ｍ－ｔｅｒｔ－ブチルフェニル基、ｐ－ｔｅｒｔ－ブチルフェニル基、３，５－ジ（ｔｅｒｔ－ブチル）フェニル基、３，５－ジ（ｔｅｒｔ－ブチル）－４－メチルフェニル基、４－ブチルフェニル基、４－ペンチルフェニル基、２，６－ビス（１－メチルエチル）フェニル基、２，４，６－トリス（１－メチルエチル）フェニル基、４－シクロヘキシルフェニル基、２，４，６－トリメチルフェニル基、４－オクチルフェニル基、４－（１，１，３，３－テトラメチルブチル）フェニル基、１－ナフチル基、２－ナフチル基、６－メチル－２－ナフチル基、５，６，７，８－テトラヒドロ－１－ナフチル基、５，６，７，８－テトラヒドロ－２－ナフチル基、フルオレニル基、フェナントリル基、アントリル基、２－ドデシルフェニル基、３－ドデシルフェニル基、４－ドデシルフェニル基、ペリレニル基、クリセニル基及びピレニル基等が挙げられる。 Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R 1 to R 4 include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2-ethylphenyl group, a 3-ethylphenyl group, a 4-ethylphenyl group, a 2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,6-dimethylphenyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 4-vinylphenyl group, an o-isopropylphenyl group, an m-isopropylphenyl group, a p-isopropylphenyl group, an o-tert-butylphenyl group, an m-tert-butylphenyl group, a p-tert-butylphenyl group, a 3,5-di(tert-butyl)phenyl group, a 3,5-di(tert-butyl)- Examples of such an alkyl group include a 4-methylphenyl group, a 4-butylphenyl group, a 4-pentylphenyl group, a 2,6-bis(1-methylethyl)phenyl group, a 2,4,6-tris(1-methylethyl)phenyl group, a 4-cyclohexylphenyl group, a 2,4,6-trimethylphenyl group, a 4-octylphenyl group, a 4-(1,1,3,3-tetramethylbutyl)phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 6-methyl-2-naphthyl group, a 5,6,7,8-tetrahydro-1-naphthyl group, a 5,6,7,8-tetrahydro-2-naphthyl group, a fluorenyl group, a phenanthryl group, an anthryl group, a 2-dodecylphenyl group, a 3-dodecylphenyl group, a 4-dodecylphenyl group, a perylenyl group, a chrysenyl group, and a pyrenyl group.
　Ｒ1～Ｒ4で表される炭素数１～２０の１価の飽和炭化水素基又は炭素数６～２０の１価の芳香族炭化水素基の置換基は、ハロゲン原子、－ＯＨ、－ＯＲ8、－ＳＯ3 -、－ＳＯ3Ｈ、－ＳＯ3 -Ｚ+、－ＣＯ2Ｈ、－ＣＯ2Ｒ8、－ＳＲ8、－ＳＯ2Ｒ8、－ＳＯ3Ｒ8又は－ＳＯ2ＮＲ9Ｒ10であってもよい。これらの置換基の中でも、－ＳＯ3 -、－ＳＯ3Ｈ、－ＳＯ3 -Ｚ+及び－ＳＯ2ＮＲ9Ｒ10からなる群から選ばれる少なくとも１種が好ましく、－ＳＯ3 -Ｚ+及び－ＳＯ2ＮＲ9Ｒ10からなる群から選ばれる少なくとも１種がより好ましい。この場合の－ＳＯ3 -Ｚ+としては、－ＳＯ3 - +Ｎ（Ｒ11）4が好ましい。 The substituent of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R 1 to R 4 may be a halogen atom, -OH, -OR 8 , -SO 3 - , -SO 3 H, -SO 3 - Z + , -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 substituents, at least one selected from the group consisting of -SO 3 - , -SO 3 H, -SO 3 - Z + and -SO 2 NR 9 R 10 is preferred, and at least one selected from the group consisting of -SO 3 - Z + and -SO 2 NR 9 R 10 is more preferred. In this case, --SO 3 --Z + is preferably --SO 3 -- + N(R 11 ) 4 .
　Ｒ1及びＲ2は、窒素原子と一緒になって窒素原子を含む環を形成してもよく、Ｒ3及びＲ4は、窒素原子と一緒になって窒素原子を含む環を形成してもよい。該窒素原子を含む環としては、例えば、以下のものが挙げられる。 R1 and R2 may form a ring containing a nitrogen atom together with the nitrogen atom, and R3 and R4 may form a ring containing a nitrogen atom together with the nitrogen atom. Examples of the ring containing a nitrogen atom include the following.
Figure JPOXMLDOC01-appb-I000009
Figure JPOXMLDOC01-appb-I000009
　－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、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、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, and an icosyloxycarbonyl group.
　－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、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、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、イコシルオキシスルホニル基等が挙げられる。 Examples of --SR 8 include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.
Examples of --SO 2 R 8 include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.
Examples of --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、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が挙げられる。 -SO 2 NR 9 R 10 is, for example, a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl 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)sulfa N-1 substituted sulfamoyl groups such as amoyl group, N-(3-methylbutyl)sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N-(1,3-dimethylbutyl)sulfamoyl group, N-(3,3-dimethylbutyl)sulfamoyl group, N-heptylsulfamoyl group, N-(1-methylhexyl)sulfamoyl group, N-(1,4-dimethylpentyl)sulfamoyl group, N-octylsulfamoyl group, N-(2-ethylhexyl)sulfamoyl group, N-(1,5-dimethyl)hexylsulfamoyl group, and N-(1,1,2,2-tetramethylbutyl)sulfamoyl group;
Examples of the sulfamoyl group include N,N-disubstituted sulfamoyl groups such as an N,N-dimethylsulfamoyl group, an N,N-ethylmethylsulfamoyl group, an N,N-diethylsulfamoyl group, an N,N-propylmethylsulfamoyl group, an N,N-isopropylmethylsulfamoyl group, an N,N-tert-butylmethylsulfamoyl group, an N,N-butylethylsulfamoyl group, an N,N-bis(1-methylpropyl)sulfamoyl group, and an N,N-heptylmethylsulfamoyl group.
　またＲ9及びＲ10で表される炭素数１～２０の１価の飽和炭化水素基の置換基は、－ＯＨ又はハロゲン原子であってもよく、該飽和炭化水素基に含まれる－ＣＨ2－は、－Ｏ－、－ＣＯ－、－ＮＨ－又は－ＮＲ8－で置き換っていてもよい。 In addition, the substituent of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R9 and R10 may be -OH or a halogen atom, and the -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, -NH- or -NR8- .
　Ｒ9及びＲ10は、互いに結合して窒素原子と一緒に３～１０員環の複素環を形成していてもよい。該複素環としては、例えば、以下のものが挙げられる。
Figure JPOXMLDOC01-appb-I000010
 R 9 and R 10 may be bonded to each other to form a 3- to 10-membered heterocycle together with the nitrogen atom. Examples of such heterocycles include the following.
Figure JPOXMLDOC01-appb-I000010
　Ｒ6及びＲ7を表す炭素数１～６のアルキル基としては、上記で挙げた直鎖状アルキル基及び分枝鎖状アルキル基のうち、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 represented by R 6 and R 7 include the above-mentioned linear alkyl groups and branched alkyl groups having 1 to 6 carbon atoms.
　Ｒ11を表す炭素数７～１０のアラルキル基としては、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 represented by R 11 include a benzyl group, a phenylethyl group, and a phenylbutyl group.
　Ｚ+は、+Ｎ（Ｒ11）4、Ｎａ+又はＫ+であり、好ましくは+Ｎ（Ｒ11）4である。
　前記+Ｎ（Ｒ11）4としては、４つのＲ11のうち、少なくとも２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、４つのＲ11の合計炭素数は２０～８０が好ましく、２０～６０がより好ましい。 Z + is + N( R11 ) 4 , Na + or K + , preferably + N( R11 ) 4 .
In the + N(R 11 ) 4 , it is preferable that at least two of the four R 11 are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R 11 is preferably 20 to 80, and more preferably 20 to 60.
　ｍは、１～４が好ましく、１又は２がより好ましい。 m is preferably 1 to 4, and more preferably 1 or 2.
　式（ＩＩ）で表される化合物（化合物（ＩＩ））は、式（ＩＩａ）で表される化合物（以下「化合物（ＩＩａ）」という場合がある。）を含むことがより好ましい。 It is more preferable that the compound represented by formula (II) (compound (II)) contains a compound represented by formula (IIa) (hereinafter sometimes referred to as "compound (IIa)").
Figure JPOXMLDOC01-appb-I000011
［式（ＩＩａ）中、Ｒ21～Ｒ24は、それぞれ独立に、水素原子、又は置換基を有していてもよい炭素数６～２０の１価の置換基を有していてもよい芳香族炭化水素基を表す。Ｒ21及びＲ22は、窒素原子と一緒になって窒素原子を含む環を形成してもよく、Ｒ23及びＲ24は、窒素原子と一緒になって窒素原子を含む環を形成してもよい。
　Ｒ25は、－ＳＯ3 -、－ＳＯ3Ｈ、－ＳＯ3 -Ｚ１+又は－ＳＯ2ＮＨＲ26を表す。
　ｍ１は、０～５の整数を表す。ｍ１が２以上の整数である場合、複数のＲ25は同一であっても異なっていてもよい。
　ａ１は、０又は１の整数を表す。
　Ｘ１は、ハロゲン原子を表す。
　Ｒ26は、炭素数１～２０の１価の飽和炭化水素基を表す。
　Ｚ１+は、+Ｎ（Ｒ27）4、Ｎａ+又はＫ+を表す。
　Ｒ27は、それぞれ独立に、炭素数１～２０の１価の飽和炭化水素基又はベンジル基を表す。］
Figure JPOXMLDOC01-appb-I000011
In formula (IIa), R 21 to R 24 each independently represent a hydrogen atom or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. R 21 and R 22 may form a ring containing a nitrogen atom together with the nitrogen atom, and R 23 and R 24 may form a ring containing a nitrogen atom together with the nitrogen atom.
R 25 represents --SO 3 -- , --SO 3 H, --SO 3 --Z1 + or --SO 2 NHR 26 .
m1 represents an integer of 0 to 5. When m1 is an integer of 2 or more, multiple R 25 may be the same or different.
a1 represents an integer of 0 or 1.
X1 represents a halogen atom.
R 26 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
Z1 + represents + N( R27 ) 4 , Na + or K + .
Each R 27 independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group.
　Ｒ21～Ｒ24で表される炭素数６～１０の１価の芳香族炭化水素基としては、前記Ｒ1～Ｒ4で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。該芳香族炭化水素基の置換基は、－ＳＯ3 -、－ＳＯ3Ｈ、－ＳＯ3 -Ｚ１+、－ＳＯ3Ｒ26又は－ＳＯ2ＮＨＲ26であってもよい。
　Ｒ21～Ｒ24の組合せとしては、Ｒ22及びＲ23が水素原子であり、Ｒ21及びＲ24が炭素数６～１０の１価の芳香族炭化水素基であり、Ｒ25が－ＳＯ3 -、－ＳＯ3Ｈ、－ＳＯ3 -Ｚ１+、－ＳＯ3Ｒ26又は－ＳＯ2ＮＨＲ26であることが好ましい。さらに好ましい組合せは、Ｒ22及びＲ23が水素原子であり、Ｒ21及びＲ24が炭素数６～１０の１価の芳香族炭化水素基であり、Ｒ25が－ＳＯ3 -、－ＳＯ3 -Ｚ１+又は－ＳＯ2ＮＨＲ26である。
　また、Ｒ21及びＲ22が、窒素原子と一緒になって窒素原子を含む脂肪族複素環を形成し、かつＲ23及びＲ24が、窒素原子と一緒になって窒素原子を含む脂肪族複素環を形成していてもよい。 Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R 21 to R 24 include the same groups as those exemplified as the aromatic hydrocarbon group for R 1 to R 4. The substituent of the aromatic hydrocarbon group may be -SO 3 - , -SO 3 H, -SO 3 - Z1 + , -SO 3 R 26 or -SO 2 NHR 26 .
A preferred combination of R 21 to R 24 is one in which R 22 and R 23 are hydrogen atoms, R 21 and R 24 are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and R 25 is -SO 3 - , -SO 3 H, -SO 3 - Z1 + , -SO 3 R 26 , or -SO 2 NHR 26. A more preferred combination is one in which R 22 and R 23 are hydrogen atoms, R 21 and R 24 are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and R 25 is -SO 3 - , -SO 3 - Z1 + , or -SO 2 NHR 26 .
In addition, R 21 and R 22 may be combined with the nitrogen atom to form an aliphatic heterocycle containing a nitrogen atom, and R 23 and R 24 may be combined with the nitrogen atom to form an aliphatic heterocycle containing a nitrogen atom.
　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 aliphatic heterocycle include the following:
Figure JPOXMLDOC01-appb-I000012
Figure JPOXMLDOC01-appb-I000012
　Ｒ26及びＲ27を表す炭素数１～２０の１価の飽和炭化水素基としては、Ｒ8～Ｒ11で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。 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 26 and R 27 include the same groups as those exemplified as the saturated hydrocarbon groups for R 8 to R 11 .
　Ｚ１+は、+Ｎ（Ｒ27）4、Ｎａ+又はＫ+であることが好ましく、より好ましくは+Ｎ（Ｒ27）4である。
　前記+Ｎ（Ｒ27）4としては、４つのＲ27のうち、少なくとも２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、４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。 Z1 + is preferably + N( R27 ) 4 , Na + or K + , more preferably + N( R27 ) 4 .
In the + N(R 27 ) 4 , it is preferable that at least two of the four R 27 are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R 27 is preferably 20 to 80, and more preferably 20 to 60.
　ｍ１は、１～４が好ましく、１又は２がより好ましい。 m1 is preferably 1 to 4, and more preferably 1 or 2.
　化合物（ＩＩａ）としては、例えば、式（１－１）～式（１－２５）で表される化合物が挙げられる。なお、式中、Ｒ26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、さらに好ましくは２－エチルヘキシル基である。これらの中でも、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又は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）及び式（１－１２）で表される化合物等が挙げられる。 Examples of the compound (IIa) include compounds represented by formulas (1-1) to (1-25). In the formula, R 26 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group. Among these, a sulfonamide of C.I. Acid Red 289, a quaternary ammonium salt of C.I. Acid Red 289, a sulfonamide of C.I. Acid Violet 102, or a quaternary ammonium salt of C.I. Acid Violet 102 is preferred. Examples of such compounds include compounds represented by formulas (1-1) to (1-8), (1-11), and (1-12).
Figure JPOXMLDOC01-appb-I000013
Figure JPOXMLDOC01-appb-I000013
Figure JPOXMLDOC01-appb-I000014
Figure JPOXMLDOC01-appb-I000014
Figure JPOXMLDOC01-appb-I000015
Figure JPOXMLDOC01-appb-I000015
Figure JPOXMLDOC01-appb-I000016
Figure JPOXMLDOC01-appb-I000016
Figure JPOXMLDOC01-appb-I000017
Figure JPOXMLDOC01-appb-I000017
Figure JPOXMLDOC01-appb-I000018
Figure JPOXMLDOC01-appb-I000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　また、化合物（ＩＩ）は、式（ＩＩＩａ）で表される化合物（以下「化合物（ＩＩＩａ）」という場合がある。）を含むこともより好ましい。 More preferably, compound (II) includes a compound represented by formula (IIIa) (hereinafter sometimes referred to as "compound (IIIa)").
Figure JPOXMLDOC01-appb-I000020
［式（ＩＩＩａ）中、Ｒ32及びＲ33は、互いに独立に、水素原子又は炭素数１～４のアルキル基を表す。
　Ｒ31及びＲ34は、互いに独立に、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又は炭素数１～４のアルキルスルホニル基を表す。
　Ｒ31及びＲ32は、窒素原子と一緒になって窒素原子を含む環を形成してもよく、Ｒ33及びＲ34は、窒素原子と一緒になって窒素原子を含む環を形成してもよい。
　ｐ及びｑは、互いに独立に、０～５の整数を表す。ｐが２以上である場合、複数のＲ31は同一でも異なってもよく、ｑが２以上である場合、複数のＲ34は同一でも異なってもよい。］
Figure JPOXMLDOC01-appb-I000020
In formula (IIIa), R 32 and R 33 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R 31 and R 34 each 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 32 may be taken together with the nitrogen atom to form a ring containing the nitrogen atom, and R 33 and R 34 may be taken together with the nitrogen atom to form a ring containing the nitrogen atom.
p and q each independently represent an integer of 0 to 5. When p is 2 or more, multiple R 31 may be the same or different, and when q is 2 or more, multiple R 34 may be the same or different.
　Ｒ31、Ｒ32、Ｒ33及びＲ34で表される炭素数１～４のアルキル基としては、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。
　Ｒ31及びＲ34で表される炭素数１～４のアルキルスルファニル基としては、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、イソプロピルスルファニル基等が挙げられる。
　Ｒ31及びＲ34で表される炭素数１～４のアルキルスルホニル基としては、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、イソプロピルスルホニル基等が挙げられる。
　Ｒ32及びＲ33は、互いに独立に、水素原子又は炭素数１～３のアルキル基が好ましく、水素原子であることがより好ましい。Ｒ31及びＲ34は、炭素数１～４のアルキル基が好ましく、メチル基がより好ましい。
　ｐ及びｑは、互いに独立に、０～２の整数が好ましく、１又は２がより好ましい。 Examples of the alkyl group having 1 to 4 carbon atoms represented by R 31 , R 32 , 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 and a tert-butyl group.
Examples of the alkylsulfanyl group having 1 to 4 carbon atoms represented by R 31 and R 34 include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, and an isopropylsulfanyl group.
Examples of the alkylsulfonyl group having 1 to 4 carbon atoms represented by R 31 and R 34 include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group.
R 32 and R 33 are each preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom. R 31 and R 34 are each preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.
p and q each independently represent preferably an integer of 0 to 2, and more preferably 1 or 2.
　化合物（ＩＩＩａ）としては、例えば、それぞれ式（１－２６）～式（１－３６）で表される化合物が挙げられる。中でも、有機溶媒への溶解性に優れる点で、式（１－２６）～式（１－３２）、式（１－３６）で表される化合物が好ましく、式（１－３６）で表される化合物（以下、式（ＩＩ－１）で表される化合物ともいう）がより好ましい。 Examples of compound (IIIa) include compounds represented by formulas (1-26) to (1-36). Among them, compounds represented by formulas (1-26) to (1-32) and (1-36) are preferred because of their excellent solubility in organic solvents, and the compound represented by formula (1-36) (hereinafter also referred to as the compound represented by formula (II-1)) is more preferred.
Figure JPOXMLDOC01-appb-I000021
Figure JPOXMLDOC01-appb-I000021
Figure JPOXMLDOC01-appb-I000022
Figure JPOXMLDOC01-appb-I000022
Figure JPOXMLDOC01-appb-I000023
Figure JPOXMLDOC01-appb-I000023
Figure JPOXMLDOC01-appb-I000024
Figure JPOXMLDOC01-appb-I000024
Figure JPOXMLDOC01-appb-I000025
Figure JPOXMLDOC01-appb-I000025
Figure JPOXMLDOC01-appb-I000026
Figure JPOXMLDOC01-appb-I000026
　着色剤（Ａ）は、式（ＩＩ）で表される化合物とは異なる着色剤を含んでいてもよい。
　異なる着色剤として染料（Ａ１）及び顔料（Ａ２）が挙げられ、顔料（Ａ２）が好ましい。これらは単独で用いてもよく、又は２種以上を組み合わせて使用してもよい。 The colorant (A) may contain a colorant different from the compound represented by formula (II).
The different colorants include dye (A1) and pigment (A2), and the pigment (A2) is preferred. These may be used alone or in combination of two or more.
　染料（Ａ１）は特に限定されず、公知の染料を使用することができ、例えば、溶剤染料、酸性染料、直接染料、媒染染料等が挙げられる。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）で染料に分類されている化合物や、染色ノート（色染社）に記載されている公知の染料が挙げられる。また、化学構造によれば、アゾ染料、シアニン染料、トリフェニルメタン染料、キサンテン染料、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、クマリン染料、キノリン染料、ニトロ染料、フタロシアニン染料、ペリレン染料、キノフタロン染料、イソインドリン染料等が挙げられる。これらのうち、有機溶剤可溶性染料が好ましい。 The dye (A1) is not particularly limited, and known dyes can be used, such as solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include compounds classified as dyes in the Color Index (published by The Society of Dyers and Colourists) and known dyes described in Dyeing Notes (Shikisensha). In addition, examples of dyes that can be used according to their chemical structure include azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, phthalocyanine dyes, perylene dyes, quinophthalone dyes, and isoindoline dyes. Of these, organic solvent-soluble dyes are preferred.
　具体的には、以下のようなカラーインデックス（Ｃ．Ｉ．）番号の染料が挙げられる。
　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、１１７、１６２、１６３、１６７、１８９；
　Ｃ．Ｉ．ソルベントレッド２４、４５、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、２１８、２２２、２２７、２３０、２４５、２４７；
　Ｃ．Ｉ．ソルベントオレンジ２、７、１１、１５、２６、４１、５４、５６、７７、８６、９９；
　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４、５、１４、１８、３５、３６、３７、３８、４４、４５、５８、５９、５９：１、６３、６７、６８、６９、７０、７８、７９、８３、９０、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、４、５、７、２８、２９、３２、３３、３４、３５；等のＣ．Ｉ．ソルベント染料、
　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．アシッドレッド１、４、８、１４、１７、１８、２６、２７、２９、３１、３３、３４、３５、３７、４０、４２、４４、５０、５１、５２、５７、６６、７３、７６、８０、８７、８８、９１、９２、９４、９５、９７、９８、１０３、１０６、１１１、１１４、１２９、１３３、１３４、１３８、１４３、１４５、１５０、１５１、１５５、１５８、１６０、１７２、１７６、１８２、１８３、１９５、１９８、２０６、２１１、２１５、２１６、２１７、２２７、２２８、２４９、２５２、２５７、２５８、２６０、２６１、２６６、２６８、２７０、２７４、２７７、２８０、２８１、２８９、３０８、３１２、３１５、３１６、３３９、３４１、３４５、３４６、３４９、３８２、３８３、３８８、３９４、４０１、４１２、４１７、４１８、４２２、４２６；
　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．アシッドバイオレット６Ｂ、７、９、１５、１６、１７、１９、２１、２３、２４、２５、３０、３４、３８、４９、７２、１０２；
　Ｃ．Ｉ．アシッドブルー１、３、５、７、９、１１、１３、１５、１７、１８、２２、２３、２４、２５、２６、２７、２９、３４、３８、４０、４１、４２、４３、４５、４８、５１、５４、５９、６０、６２、７０、７２、７４、７５、７８、８０、８２、８３、８６、８７、８８、９０、９０：１、９１、９２、９３、９３：１、９６、９９、１００、１０２、１０３、１０４、１０８、１０９、１１０、１１２、１１３、１１７、１１９、１２０、１２３、１２６、１２７、１２９、１３０、１３１、１３８、１４０、１４２、１４３、１４７、１５０、１５１、１５４、１５８、１６１、１６６、１６７、１６８、１７０、１７１、１７５、１８２、１８３、１８４、１８７、１９２、１９９、２０３、２０４、２０５、２１０、２１３、２２９、２３４、２３６、２４２、２４３、２４９、２５６、２５９、２６７、２６９、２７８、２８０、２８５、２９０、２９６、３１５、３２４：１、３３５、３４０；
　Ｃ．Ｉ．アシッドグリーン１、３、５、６、７、８、９、１１、１３、１４、１５、１６、２２、２５、２７、２８、４１、５０、５０：１、５８、６３、６５、８０、１０４、１０５、１０６、１０９；等のＣ．Ｉ．アシッド染料、
　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．ダイレクトレッド７９、８２、８３、８４、９１、９２、９６、９７、９８、９９、１０５、１０６、１０７、１７２、１７３、１７６、１７７、１７９、１８１、１８２、１８４、２０４、２０７、２１１、２１３、２１８、２２０、２２１、２２２、２３２、２３３、２３４、２４１、２４３、２４６、２５０；
　Ｃ．Ｉ．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．ダイレクトバイオレット４７、５２、５４、５９、６０、６５、６６、７９、８０、８１、８２、８４、８９、９０、９３、９５、９６、１０３、１０４；
　Ｃ．Ｉ．ダイレクトブルー１、２、３、６、８、１５、２２、２５、２８、２９、４０、４１、４２、４７、５２、５５、５７、７１、７６、７７、７８、８０、８１、８４、８５、８６、８７、９０、９３、９４、９５、９７、９８、９９、１００、１０１、１０６、１０７、１０８、１０９、１１３、１１４、１１５、１１７、１１９、１２０、１３７、１４９、１５０、１５３、１５５、１５６、１５８、１５９、１６０、１６１、１６２、１６３、１６４、１６５、１６６、１６７、１６８、１７０、１７１、１７２、１７３、１８８、１８９、１９０、１９２、１９３、１９４、１９５、１９６、１９８、１９９、２００、２０１、２０２、２０３、２０７、２０９、２１０、２１２、２１３、２１４、２２２、２２５、２２６、２２８、２２９、２３６、２３７、２３８、２４２、２４３、２４４、２４５、２４６、２４７、２４８、２４９、２５０、２５１、２５２、２５６、２５７、２５９、２６０、２６８、２７４、２７５、２９３；
　Ｃ．Ｉ．ダイレクトグリーン２５、２７、３１、３２、３４、３７、６３、６５、６６、６７、６８、６９、７２、７９、８２；等のＣ．Ｉ．ダイレクト染料、
　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、６；０等のＣ．Ｉ．ディスパース染料、
　Ｃ．Ｉ．ベーシックレッド１、１０；
　Ｃ．Ｉ．ベーシックブルー１、３、５、７、９、１９、２１、２２、２４、２５、２６、２８、２９、４０、４１、４５、４７、５４、５８、５９、６０、６４、６５、６６、６７、６８、８１、８３、８８、８９；
　Ｃ．Ｉ．ベーシックバイオレット２；
　Ｃ．Ｉ．ベーシックレッド９；
　Ｃ．Ｉ．ベーシックグリーン１；等のＣ．Ｉ．ベーシック染料、
　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；
　Ｃ．Ｉ．リアクティブレッド３６；等のＣ．Ｉ．リアクティブ染料、
　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．モーダントレッド１、２、３、４、９、１１、１２、１４、１７、１８、１９、２２、２３、２４、２５、２６、２７、２９、３０、３２、３３、３６、３７、３８、３９、４１、４２、４３、４５、４６、４８、５２、５３、５６、６２、６３、７１、７４、７６、７８、８５、８６、８８、９０、９４、９５；
　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；
　Ｃ．Ｉ．モーダントバイオレット１、１：１、２、３、４、５、６、７、８、１０、１１、１４、１５、１６、１７、１８、１９、２１、２２、２３、２４、２７、２８、３０、３１、３２、３３、３６、３７、３９、４０、４１、４４、４５、４７、４８、４９、５３、５８；
　Ｃ．Ｉ．モーダントブルー１、２、３、７、８、９、１２、１３、１５、１６、１９、２０、２１、２２、２３、２４、２６、３０、３１、３２、３９、４０、４１、４３、４４、４８、４９、５３、６１、７４、７７、８３、８４；
　Ｃ．Ｉ．モーダントグリーン１、３、４、５、１０、１３、１５、１９、２１、２３、２６、２９、３１、３３、３４、３５、４１、４３、５３；等のＣ．Ｉ．モーダント染料、
　Ｃ．Ｉ．バットグリーン１；等のＣ．Ｉ．バット染料等 Specifically, dyes having the following Color Index (C.I.) numbers are included.
C.I. Solvent Yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 117, 162, 163, 167, 189;
C.I. Solvent Red 24, 45, 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, 218, 222, 227, 230, 245, 247;
C.I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 77, 86, 99;
C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;
C.I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 38, 44, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
C.I. Solvent dyes such as C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35;
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, 1 57,160,161,163,168,169,172,177,178,179,184,190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,24 0, 242, 243, 251;
C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 18 2, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341 , 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;
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 Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;
C.I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90: 1, 91, 92, 93, 93: 1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126,127,129,130,131,138,140,142,143,147,150,151,154,158,161,166,167,168,170,171,175,182,183,184,187,192,199,203,204,205,2 10, 213, 229, 234, 236, 242, 243, 249, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340;
C. I. Acid dyes such as C. I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109;
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 Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
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 Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C.I. Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 87, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166 , 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;
C.I. Direct dyes such as C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82;
C.I. Disperse Yellow 51, 54, 76;
C.I. Disperse Violet 26, 27;
C.I. Disperse dyes such as C.I. Disperse Blue 1, 14, 56, 6;0,
C.I. Basic Red 1, 10;
C.I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89;
C.I. Basic Violet 2;
C.I. Basic Red 9;
C.I. Basic dyes such as C.I. Basic Green 1;
C.I. Reactive Yellow 2, 76, 116;
C.I. Reactive Orange 16;
C.I. Reactive dyes such as C.I. Reactive Red 36;
C.I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C.I. Mordant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;
C.I. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C.I. Mordant Violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58;
C.I. Mordant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;
C.I. Mordant dyes such as C.I. Mordant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53;
C.I. Vat dyes such as C.I. Vat Green 1;
　これらの染料は、所望する光学フィルタの分光スペクトルに合わせて適宜選択すればよい。 These dyes can be selected appropriately to match the optical spectrum of the desired optical filter.
　顔料（Ａ２）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）でピグメントに分類されている顔料が挙げられる。また、化学構造によれば、アゾ系顔料、シアニン系顔料、トリフェニルメタン系顔料、キサンテン系顔料、アントラキノン系顔料、ナフトキノン系顔料、キノンイミン系顔料、メチン系顔料、アゾメチン系顔料、スクアリリウム系顔料、アクリジン系顔料、スチリル系顔料、クマリン系顔料、キノリン系顔料、ニトロ系顔料、フタロシアニン系顔料、ペリレン系顔料、キノフタロン系顔料、イソインドリン系顔料等が挙げられる。これらのうち、フタロシアニン系顔料、キノフタロン系顔料、イソインドリン系顔料等が好ましい。 Pigments (A2) may be any known pigment, including, for example, pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists). In addition, according to their chemical structure, examples include azo pigments, cyanine pigments, triphenylmethane pigments, xanthene pigments, anthraquinone pigments, naphthoquinone pigments, quinoneimine pigments, methine pigments, azomethine pigments, squarylium pigments, acridine pigments, styryl pigments, coumarin pigments, quinoline pigments, nitro pigments, phthalocyanine pigments, perylene pigments, quinophthalone pigments, and isoindoline pigments. Of these, phthalocyanine pigments, quinophthalone pigments, and isoindoline pigments are preferred.
　ピグメントに分類されている顔料としては、具体的には、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、１８５、１９４、２１４、２３１等の黄色顔料；
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等の橙色顔料；
Ｃ．Ｉ．ピグメントレッド９、９７、１０５、１２２、１２３、１４４、１４９、１６６、１６８、１７６、１７７、１７８、１７９、１８０、１９０、１９２、２０２、２０９、２１５、２１６、２２４、２４２、２５４、２５５、２６４、２６５、２６６、２６８、２６９、２７３、２９１等の赤色顔料；
Ｃ．Ｉ．ピグメントブルー１５、１５：１、１５：２、１５：３、１５：４、１５：６、１６、６０等の青色顔料；
Ｃ．Ｉ．ピグメントバイオレット１、１９、２３、２９、３２、３６、３８等の紫色顔料；
Ｃ．Ｉ．ピグメントグリーン７、３６、５８、５９、６２、６３等の緑色顔料；
Ｃ．Ｉ．ピグメントブラウン２３、２５等の茶色顔料；
Ｃ．Ｉ．ピグメントブラック１、７、３１、３２等の黒色顔料；等が挙げられる。 Specific examples of pigments classified as C.I. Pigment include yellow pigments such as 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, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, and 231;
Orange pigments such as C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
red pigments such as C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 178, 179, 180, 190, 192, 202, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273, 291;
blue pigments such as C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60;
purple pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38;
green pigments such as C.I. Pigment Green 7, 36, 58, 59, 62, 63;
Brown pigments such as C.I. Pigment Brown 23 and 25;
black pigments such as C.I. Pigment Black 1, 7, 31, and 32;
　これらの顔料は、所望する光学フィルタの分光スペクトルに合わせて適宜選択すればよい。 These pigments can be selected appropriately to match the optical spectrum of the desired optical filter.
　式（ＩＩ）で表される化合物の含有率は、着色剤総量中、好ましくは６０質量％以上、より好ましくは７０質量％以上、さらに好ましくは８０質量％以上、さらにより好ましくは９０質量％以上、特に好ましくは１００質量％である。 The content of the compound represented by formula (II) in the total amount of the colorant is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 100% by mass.
　着色硬化性樹脂組成物が溶剤（Ｅ）を含む場合、予め着色剤（Ａ）と溶剤（Ｅ）とを含む着色剤含有液を調製した後、該着色剤含有液を使用して着色硬化性樹脂組成物を調製してもよい。着色剤（Ａ）が溶剤（Ｅ）に溶解しない場合、例えば着色剤（Ａ）が顔料（Ａ２）を含む場合等には、着色剤含有液は、着色剤（Ａ）を溶剤（Ｅ）に分散させて混合することにより調製できる。着色剤含有液は、着色硬化性樹脂組成物に含有される溶剤（Ｅ）の一部又は全部を含んでいてもよい。 When the colored curable resin composition contains a solvent (E), a colorant-containing liquid containing the colorant (A) and the solvent (E) may be prepared in advance, and then the colorant-containing liquid may be used to prepare the colored curable resin composition. When the colorant (A) is not soluble in the solvent (E), for example when the colorant (A) contains a pigment (A2), the colorant-containing liquid can be prepared by dispersing the colorant (A) in the solvent (E) and mixing. The colorant-containing liquid may contain a part or all of the solvent (E) contained in the colored curable resin composition.
　着色剤含有液中の固形分の含有率は、着色剤含有液の総量に対して、１００質量％未満であり、好ましくは１質量％以上８０質量％以下、より好ましくは２質量％以上７０質量％以下、さらに好ましくは５質量％以上６５質量％以下である。 The solid content in the colorant-containing liquid is less than 100% by mass, preferably 1% by mass to 80% by mass, more preferably 2% by mass to 70% by mass, and even more preferably 5% by mass to 65% by mass, based on the total amount of the colorant-containing liquid.
　着色剤含有液中の着色剤（Ａ）の含有率は、着色剤含有液中の固形分の総量に対して、１００質量％未満であり、好ましくは０．５質量％以上８０質量％以下であり、より好ましくは１質量％以上７０質量％以下であり、さらに好ましくは２．５質量％以上６５質量％以下である。 The content of colorant (A) in the colorant-containing liquid is less than 100% by mass, preferably 0.5% by mass to 80% by mass, more preferably 1% by mass to 70% by mass, and even more preferably 2.5% by mass to 65% by mass, based on the total amount of solids in the colorant-containing liquid.
　着色剤（Ａ）は、必要に応じて、ロジン処理、酸性基又は塩基性基が導入された誘導体等を用いた表面処理、高分子化合物等による着色剤（Ａ）表面へのグラフト処理、硫酸微粒化法、ソルトミリング法等による微粒化処理、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。着色剤（Ａ）の粒径は、略均一であることが好ましい。 If necessary, the colorant (A) may be subjected to a rosin treatment, a surface treatment using a derivative having an acidic or basic group introduced therein, a grafting treatment to the surface of the colorant (A) using a polymer compound, a micronization treatment using a sulfuric acid micronization method or a salt milling method, a washing treatment using an organic solvent or water to remove impurities, a removal treatment using an ion exchange method for ionic impurities, etc. It is preferable that the particle size of the colorant (A) is approximately uniform.
　着色剤（Ａ）は、分散剤を含有させて分散処理を行うことで、着色剤（Ａ）が溶液中で均一に分散した状態にすることができる。着色剤（Ａ）として２種以上を組み合わせて使用する場合は、それぞれを単独で分散処理してもよく、複数種を混合して分散処理してもよい。 The colorant (A) can be made to be uniformly dispersed in the solution by adding a dispersant and carrying out a dispersion treatment. When using a combination of two or more types of colorant (A), each may be dispersed alone, or multiple types may be mixed and dispersed.
　分散剤としては、例えば、界面活性剤等が挙げられ、カチオン系、アニオン系、ノニオン系及び両性のいずれの界面活性剤であってもよい。具体的にはポリエステル系、ポリアミン系及びアクリル系等の界面活性剤等が挙げられる。これらの分散剤は、単独で又は２種以上を組み合わせて用いてもよい。分散剤としては、商品名で表すと、ＫＰ（信越化学工業（株）製）、フローレン（共栄社化学（株）製）、ソルスパース（登録商標）（ゼネカ（株）製）、ＥＦＫＡ（登録商標）（ＢＡＳＦ社製）、アジスパー（登録商標）（味の素ファインテクノ（株）製）及びＤｉｓｐｅｒｂｙｋ（登録商標）（ビックケミー（株）製）、ＢＹＫ（登録商標）（ビックケミー（株）製）等が挙げられる。また、分散剤として、後述する樹脂（Ｂ）を使用してもよい。 The dispersant may be, for example, a surfactant, which may be any of cationic, anionic, nonionic, and amphoteric surfactants. Specific examples include polyester, polyamine, and acrylic surfactants. These dispersants may be used alone or in combination of two or more. Examples of dispersants by trade name include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLORENE (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Corporation), EFKA (registered trademark) (manufactured by BASF), AJISPER (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), and BYK (registered trademark) (manufactured by BYK-Chemie Co., Ltd.). Resin (B), which will be described later, may also be used as the dispersant.
　分散剤を用いる場合、該分散剤（固形分）の使用量は、着色剤含有液中の着色剤（Ａ）１００質量部に対して、通常１質量部以上１００００質量部以下であり、好ましくは５質量部以上５０００質量部以下であり、より好ましくは１０質量部以上１０００質量部以下であり、さらに好ましくは１５質量部以上８００質量部以下である。該分散剤の使用量が前記の範囲にあると、より均一な分散状態の着色剤含有液（以下、着色剤分散液又は顔料分散液という場合がある）が得られる傾向がある。 When a dispersant is used, the amount of the dispersant (solid content) used is usually 1 part by mass to 10,000 parts by mass, preferably 5 parts by mass to 5,000 parts by mass, more preferably 10 parts by mass to 1,000 parts by mass, and even more preferably 15 parts by mass to 800 parts by mass, per 100 parts by mass of colorant (A) in the colorant-containing liquid. When the amount of the dispersant used is within the above range, a colorant-containing liquid (hereinafter sometimes referred to as a colorant dispersion or pigment dispersion) in a more uniformly dispersed state tends to be obtained.
　着色剤（Ａ）と溶剤（Ｅ）とを含む着色剤含有液を予め調製した後、該着色剤含有液を使用して着色硬化性樹脂組成物を調製する場合、着色剤含有液は、着色硬化性樹脂組成物に含有される樹脂（Ｂ）の一部又は全部、好ましくは一部を予め含んでいてもよい。樹脂（Ｂ）を予め含ませておくことで、着色剤含有液の分散安定性をさらに改善できる。 When a colorant-containing liquid containing a colorant (A) and a solvent (E) is prepared in advance and then the colorant-containing liquid is used to prepare a colored curable resin composition, the colorant-containing liquid may already contain a part or all, preferably a part, of the resin (B) contained in the colored curable resin composition. By including the resin (B) in advance, the dispersion stability of the colorant-containing liquid can be further improved.
　着色剤含有液が樹脂（Ｂ）を含有する場合、樹脂（Ｂ）の含有量は、着色剤含有液中の着色剤（Ａ）１００質量部に対して、例えば、１０質量部以上１００００質量部以下であり、２０質量部以上５０００質量部以下が好ましく、２５質量部以上２５００質量部以下がより好ましい。 When the colorant-containing liquid contains resin (B), the content of resin (B) is, for example, 10 parts by mass or more and 10,000 parts by mass or less, preferably 20 parts by mass or more and 5,000 parts by mass or less, and more preferably 25 parts by mass or more and 2,500 parts by mass or less, relative to 100 parts by mass of colorant (A) in the colorant-containing liquid.
　着色剤（Ａ）の含有率は、着色硬化性樹脂組成物の固形分の総量中、好ましくは１質量％以上９３質量％以下であり、より好ましくは１０質量％以上９１質量％以下であり、さらに好ましくは１５質量％以上８９質量％以下であり、よりさらに好ましくは１８質量％以上８７質量％以下である。着色剤（Ａ）の含有率が前記の範囲にあると、光学フィルタとしたときの色濃度が十分であり、かつ組成物中に樹脂（Ｂ）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パターンを形成することができることから好ましい。
　ここで、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。固形分の総量及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又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 mass or more and 93% by mass or less, more preferably 10% by mass or more and 91% by mass or less, even more preferably 15% by mass or more and 89% by mass or less, and even more preferably 18% by mass or more and 87% by mass or less, based on the total amount of solids in the colored curable resin composition. When the content of the colorant (A) is within the above range, the color density when made into an optical filter is sufficient, and the necessary amount of the resin (B) can be contained in the composition, so that a pattern with sufficient mechanical strength can be formed, which is preferable.
Here, the "total amount of solids" in this specification refers to the amount obtained by subtracting the content of the solvent from the total amount of the colored curable resin composition. The total amount of solids and the content of each component relative thereto can be measured by a known analytical means such as liquid chromatography or gas chromatography.
＜樹脂（Ｂ）＞
　樹脂（Ｂ）は、特に限定されないが、アルカリ可溶性樹脂であることが好ましい。樹脂（Ｂ）としては、以下の樹脂［Ｋ１］～［Ｋ６］等が挙げられ、樹脂［Ｋ１］から［Ｋ６］から選ばれる少なくとも１つであることが好ましい。
　樹脂［Ｋ１］；不飽和カルボン酸及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１種の単量体（ａ）（以下「（ａ）」という場合がある）に由来する構造単位と、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（ｂ）（以下「（ｂ）」という場合がある）に由来する構造単位とを有する共重合体；
　樹脂［Ｋ２］；前記（ａ）に由来する構造単位と前記（ｂ）に由来する構造単位と、（ａ）と共重合可能な単量体（ｃ）（ただし、（ａ）及び（ｂ）とは異なる。）（以下「（ｃ）」という場合がある）に由来する構造単位とを有する共重合体；
　樹脂［Ｋ３］；前記（ａ）に由来する構造単位と前記（ｃ）に由来する構造単位とを有する共重合体；
　樹脂［Ｋ４］；前記（ａ）に由来する構造単位に前記（ｂ）を付加させた構造単位と前記（ｃ）に由来する構造単位とを有する共重合体であり、（ｂ）が付加しない（ａ）に由来する構造単位を含む共重合体； 
　樹脂［Ｋ４’］；前記（ａ）に由来する構造単位に前記（ｂ）を付加させた構造単位と前記（ｃ）に由来する構造単位とを有する共重合体であり、（ｂ）が付加しない（ａ）に由来する構造単位を含まない；
　樹脂［Ｋ５］；前記（ｂ）に由来する構造単位に前記（ａ）を付加させた構造単位と前記（ｃ）に由来する構造単位とを有する共重合体（（ａ）が付加しない（ｂ）に由来する構造単位を含んでもよいが、含まないことが好ましい）；
　樹脂［Ｋ６］；前記（ｂ）に由来する構造単位に前記（ａ）を付加させ、カルボン酸無水物をさらに付加させた構造単位と前記（ｃ）に由来する構造単位とを有する共重合体。 <Resin (B)>
Resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of resin (B) include the following resins [K1] to [K6], and it is preferably at least one selected from resins [K1] to [K6].
Resin [K1]: a copolymer having a structural unit derived from at least one monomer (a) (hereinafter sometimes referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a structural unit derived from a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond;
Resin [K2]: a copolymer having a structural unit derived from the (a), a structural unit derived from the (b), and a structural unit derived from a monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter, may be referred to as "(c)");
Resin [K3]: a copolymer having a structural unit derived from the (a) and a structural unit derived from the (c);
Resin [K4]: a copolymer having a structural unit derived from the (a) to which the (b) is added and a structural unit derived from the (c), the copolymer including a structural unit derived from the (a) to which the (b) is not added;
Resin [K4']: a copolymer having a structural unit derived from the (a) to which the (b) is added and a structural unit derived from the (c), and not containing a structural unit derived from the (a) to which the (b) is not added;
Resin [K5]: a copolymer having a structural unit derived from the (b) to which the (a) has been added and a structural unit derived from the (c) (which may contain, but preferably does not contain, a structural unit derived from the (b) to which the (a) has not been added);
Resin [K6]: A copolymer having a structural unit obtained by adding the (a) to a structural unit derived from the (b) and further adding a carboxylic acid anhydride, and a structural unit derived from the (c).
　（ａ）としては、具体的には、例えば、アクリル酸、メタクリル酸、クロトン酸、ｏ－、ｍ－、ｐ－ビニル安息香酸等の不飽和モノカルボン酸類；
　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、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類；
　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－５－メチルビシクロ［２．２．１］ヘプト－２－エン、５－カルボキシ－５－エチルビシクロ［２．２．１］ヘプト－２－エン、５－カルボキシ－６－メチルビシクロ［２．２．１］ヘプト－２－エン、５－カルボキシ－６－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類；
　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、５，６－ジカルボキシビシクロ［２．２．１］ヘプト－２－エン無水物等の不飽和ジカルボン酸類無水物；
　こはく酸モノ〔２－（メタ）アクリロイルオキシエチル〕、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）アクリル酸のような、同一分子中にヒドロキシ基及びカルボキシ基を含有する不飽和アクリレート類等が挙げられる。
　これらのうち、共重合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、無水マレイン酸等が好ましい。 Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Unsaturated dicarboxylic acids such as 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, dimethyltetrahydrophthalic acid, and 1,4-cyclohexenedicarboxylic acid;
Bicyclounsaturated compounds containing a carboxy group, such as methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;
Unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride;
Unsaturated mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids, such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate;
Examples include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid.
Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferred from the standpoint of copolymerization reactivity and solubility of the resulting resin in an aqueous alkaline solution.
　（ｂ）は、例えば、炭素数２～４の環状エーテル構造（例えば、オキシラン環、オキセタン環及びテトラヒドロフラン環からなる群から選ばれる少なくとも１種）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。（ｂ）は、炭素数２～４の環状エーテルと（メタ）アクリロイルオキシ基とを有する単量体が好ましい。
　尚、本明細書において、「（メタ）アクリル酸」とは、アクリル酸及びメタクリル酸よりなる群から選ばれる少なくとも１種を表す。「（メタ）アクリロイル」及び「（メタ）アクリレート」等の表記も、同様の意味を有する。 (b) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.
In this specification, the term "(meth)acrylic acid" refers to at least one selected from the group consisting of acrylic acid and methacrylic acid. The terms "(meth)acryloyl" and "(meth)acrylate" have the same meaning.
　（ｂ）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（ｂ１）（以下「（ｂ１）」という場合がある）、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（ｂ２）（以下「（ｂ２）」という場合がある）、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（ｂ３）（以下「（ｂ３）」という場合がある）等が挙げられる。 Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b2)"), and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), etc.
　（ｂ１）としては、例えば、直鎖状又は分枝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（ｂ１－１）（以下「（ｂ１－１）」という場合がある）、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（ｂ１－２）（以下「（ｂ１－２）」という場合がある）が挙げられる。 Examples of (b1) include monomer (b1-1) (hereinafter sometimes referred to as "(b1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, and monomer (b1-2) (hereinafter sometimes referred to as "(b1-2)") having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized.
　（ｂ１－１）としては、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、ｏ－ビニルベンジルグリシジルエーテル、ｍ－ビニルベンジルグリシジルエーテル、ｐ－ビニルベンジルグリシジルエーテル、α－メチル－ｏ－ビニルベンジルグリシジルエーテル、α－メチル－ｍ－ビニルベンジルグリシジルエーテル、α－メチル－ｐ－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、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。 (b1-1) includes glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyl Examples of such styrene include 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.
　（ｂ１－２）としては、ビニルシクロヘキセンモノオキサイド、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２０００；（株）ダイセル製）、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Ａ４００；（株）ダイセル製）、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Ｍ１００；（株）ダイセル製）、式（ＢＩ）で表される化合物及び式（ＢＩＩ）で表される化合物等が挙げられる。 (b1-2) includes vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Corporation), compounds represented by formula (BI) and compounds represented by formula (BII).
Figure JPOXMLDOC01-appb-I000027
Figure JPOXMLDOC01-appb-I000027
［式（ＢＩ）及び式（ＢＩＩ）中、Ｒe及びＲfは、水素原子、又は炭素数１～４のアルキル基を表し、該アルキル基に含まれる水素原子は、ヒドロキシ基で置換されていてもよい。
　Ｘe及びＸfは、単結合、＊－Ｒg－、＊－Ｒg－Ｏ－、＊－Ｒg－Ｓ－又は＊－Ｒg－ＮＨ－を表す。
　Ｒgは、炭素数１～６のアルカンジイル基を表す。
　＊は、Ｏとの結合手を表す。］ In formula (BI) and formula (BII), R e and R f represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group.
X e and X f each represent a single bond, *-R g -, *-R g -O-, *-R g -S- or *-R g -NH-.
R g represents an alkanediyl group having 1 to 6 carbon atoms.
* represents a bond to O.
　炭素数１～４のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基等が挙げられる。
　水素原子がヒドロキシで置換されたアルキル基としては、ヒドロキシメチル基、１－ヒドロキシエチル基、２－ヒドロキシエチル基、１－ヒドロキシプロピル基、２－ヒドロキシプロピル基、３－ヒドロキシプロピル基、１－ヒドロキシ－１－メチルエチル基、２－ヒドロキシ－１－メチルエチル基、１－ヒドロキシブチル基、２－ヒドロキシブチル基、３－ヒドロキシブチル基、４－ヒドロキシブチル基等が挙げられる。
　Ｒe及びＲfとしては、好ましくは水素原子、メチル基、ヒドロキシメチル基、１－ヒドロキシエチル基、２－ヒドロキシエチル基が挙げられ、より好ましくは水素原子、メチル基が挙げられる。 Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxy group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
R e and R f are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.
　アルカンジイル基としては、メチレン基、エチレン基、プロパン－１，２－ジイル基、プロパン－１，３－ジイル基、ブタン－１，４－ジイル基、ペンタン－１，５－ジイル基、ヘキサン－１，６－ジイル基等が挙げられる。
　Ｘe及びＸfとしては、好ましくは単結合、メチレン基、エチレン基、＊－ＣＨ2－Ｏ－及び＊－ＣＨ2ＣＨ2－Ｏ－が挙げられ、より好ましくは単結合、＊－ＣＨ2ＣＨ2－Ｏ－が挙げられる（＊はＯとの結合手を表す）。 Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group.
X e and X f are preferably a single bond, a methylene group, an ethylene group, *-CH 2 -O-, and *-CH 2 CH 2 -O-, and more preferably a single bond or *-CH 2 CH 2 -O- (* represents a bond to O).
　式（ＢＩ）で表される化合物としては、式（ＢＩ－１）～式（ＢＩ－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（ＢＩ－１）、式（ＢＩ－３）、式（ＢＩＩ－５）、式（ＢＩ－７）、式（ＢＩ－９）又は式（ＢＩ－１１）～式（ＢＩ－１５）で表される化合物が好ましく、式（ＢＩ－１）、式（ＢＩ－７）、式（ＢＩ－９）又は式（ＢＩ－１５）で表される化合物がより好ましい。 The compound represented by formula (BI) includes compounds represented by any of formulas (BI-1) to (BI-15). Among them, compounds represented by formulas (BI-1), (BI-3), (BII-5), (BI-7), (BI-9) or (BI-11) to (BI-15) are preferred, and compounds represented by formulas (BI-1), (BI-7), (BI-9) or (BI-15) are more preferred.
Figure JPOXMLDOC01-appb-I000028
Figure JPOXMLDOC01-appb-I000028
　式（ＢＩＩ）で表される化合物としては、式（ＢＩＩ－１）～式（ＢＩＩ－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（ＢＩＩ－１）、式（ＢＩＩ－３）、式（ＢＩＩ－５）、式（ＢＩＩ－７）、式（ＢＩＩ－９）又は式（ＢＩＩ－１１）～式（ＢＩＩ－１５）で表される化合物が好ましく、式（ＢＩＩ－１）、式（ＢＩＩ－７）、式（ＢＩＩ－９）又は式（ＢＩＩ－１５）で表される化合物がより好ましい。 The compound represented by formula (BII) includes compounds represented by any of formulas (BII-1) to (BII-15). Among them, compounds represented by formulas (BII-1), (BII-3), (BII-5), (BII-7), (BII-9) or (BII-11) to (BII-15) are preferred, and compounds represented by formulas (BII-1), (BII-7), (BII-9) or (BII-15) are more preferred.
Figure JPOXMLDOC01-appb-I000029
Figure JPOXMLDOC01-appb-I000029
　式（ＢＩ）で表される化合物及び式（ＢＩＩ）で表される化合物は、それぞれ単独で用いても、２種以上を併用してもよい。式（ＢＩ）で表される化合物及び式（ＢＩＩ）で表される化合物を併用する場合、これらの含有比率〔式（ＢＩ）で表される化合物：式（ＢＩＩ）で表される化合物〕はモル基準で、好ましくは５：９５～９５：５、より好ましくは２０：８０～８０：２０である。 The compound represented by formula (BI) and the compound represented by formula (BII) may be used alone or in combination of two or more kinds. When the compound represented by formula (BI) and the compound represented by formula (BII) are used in combination, the content ratio thereof [compound represented by formula (BI): compound represented by formula (BII)] is preferably 5:95 to 95:5, more preferably 20:80 to 80:20 on a molar basis.
　（ｂ２）としては、オキセタニル基と（メタ）アクリロイルオキシ基とを有する単量体がより好ましい。（ｂ２）としては、３－メチル－３－メタクリルロイルオキシメチルオキセタン、３－メチル－３－アクリロイルオキシメチルオキセタン、３－エチル－３－メタクリロイルオキシメチルオキセタン、３－エチル－３－アクリロイルオキシメチルオキセタン、３－メチル－３－メタクリロイルオキシエチルオキセタン、３－メチル－３－アクリロイルオキシエチルオキセタン、３－エチル－３－メタクリロイルオキシエチルオキセタン、３－エチル－３－アクリロイルオキシエチルオキセタン等が挙げられる。 More preferably, (b2) is a monomer having an oxetanyl group and a (meth)acryloyloxy group. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, and the like.
　（ｂ３）としては、テトラヒドロフリル基と（メタ）アクリロイルオキシ基とを有する単量体がより好ましい。（ｂ３）としては、具体的には、テトラヒドロフルフリルアクリレート（例えば、ビスコートＶ＃１５０、大阪有機化学工業（株）製）、テトラヒドロフルフリルメタクリレート等が挙げられる。 As (b3), a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, etc.
　（ｂ）としては、得られる光学フィルタの耐熱性、耐薬品性等の信頼性をより高くすることができる点で、（ｂ１）であることが好ましい。さらに、着色硬化性樹脂組成物の保存安定性が優れるという点で、（ｂ１－２）がより好ましい。 As (b), (b1) is preferable since it can improve the reliability of the heat resistance, chemical resistance, etc. of the obtained optical filter. Furthermore, (b1-2) is more preferable since it provides excellent storage stability of the colored curable resin composition.
　（ｃ）としては、（メタ）アクリル酸エステル系モノマー、不飽和ジカルボン酸エステルなどの不飽和カルボン酸エステル類；不飽和脂肪族炭化水素環、不飽和複素環、または芳香族環を有するビニルモノマーなどが挙げられる。
　（メタ）アクリル酸エステル系モノマーとしては、例えば、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）アクリレートなどの直鎖又は分岐鎖の脂肪族飽和炭化水素基を有する（メタ）アクリル酸エステル類；
　アリル（メタ）アクリレート、プロパルギル（メタ）アクリレートなどの直鎖又は分岐鎖の脂肪族不飽和炭化水素基を有する（メタ）アクリル酸エステル類；
　シクロヘキシル（メタ）アクリレート、２－メチルシクロヘキシル（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（当該技術分野では、慣用名として「ジシクロペンタニル（メタ）アクリレート」といわれている。また、「トリシクロデシル（メタ）アクリレート」という場合がある。）、イソボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレートなどの環状飽和炭化水素基を有する（メタ）アクリル酸エステル類；
　トリシクロ［５．２．１．０2,6］デセン－８－イル（メタ）アクリレート（当該技術分野では、慣用名として「ジシクロペンテニル（メタ）アクリレート」といわれている。）、ジシクロペンタニルオキシエチル（メタ）アクリレートなどの環状不飽和脂肪族炭化水素基を有する（メタ）アクリル酸エステル類；
　フェニル（メタ）アクリレート、ナフチル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシベンジル（メタ）アクリレート等の芳香族環を有する（メタ）アクリル酸エステル類；
　２－ヒドロキシエチル（メタ）アクリレート、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）アクリル酸エステル類が挙げられる。
　不飽和ジカルボン酸エステルとしては、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等のジカルボン酸ジエステルが挙げられる。 Examples of (c) include (meth)acrylic acid ester monomers, unsaturated carboxylates such as unsaturated dicarboxylates, and vinyl monomers having an unsaturated aliphatic hydrocarbon ring, an unsaturated heterocycle, or an aromatic ring.
Examples of (meth)acrylic acid ester monomers include (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group, such as 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, and cyclopentyl (meth)acrylate;
(meth)acrylic acid esters having a linear or branched aliphatic unsaturated hydrocarbon group, such as allyl (meth)acrylate and propargyl (meth)acrylate;
(meth)acrylic acid esters having a cyclic saturated hydrocarbon group, such as cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 ]decan-8-yl (meth)acrylate (commonly known in the technical field as "dicyclopentanyl (meth)acrylate" and sometimes called "tricyclodecyl (meth)acrylate"), isobornyl (meth)acrylate, and adamantyl (meth)acrylate;
(meth)acrylic acid esters having a cyclic unsaturated aliphatic hydrocarbon group, such as tricyclo[5.2.1.0 2,6 ]decen-8-yl(meth)acrylate (commonly known as "dicyclopentenyl(meth)acrylate" in the technical field), and dicyclopentanyloxyethyl(meth)acrylate;
(meth)acrylic acid esters having an aromatic ring, such as phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate, and phenoxybenzyl (meth)acrylate;
Examples of the hydroxyl group-containing (meth)acrylic acid esters include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.
Examples of the unsaturated dicarboxylic acid ester include dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate.
　これらの不飽和カルボン酸エステル類のうち、メチルメタクリレート、２－エチルヘキシルアクリレートなどのＣ1-10アルキル（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）アクリレートなどの環状飽和炭化水素基を有する（メタ）アクリル酸エステル類；
　トリシクロ［５．２．１．０2,6］デセン－８－イル（メタ）アクリレートなどの環状不飽和脂肪族炭化水素基を有する（メタ）アクリル酸エステル類；
　ベンジル（メタ）アクリレート、フェノキシベンジル（メタ）アクリレート等の芳香族環を有する（メタ）アクリル酸エステル類などが好ましい。 Among these unsaturated carboxylic acid esters, C 1-10 alkyl (meth)acrylates such as methyl methacrylate and 2-ethylhexyl acrylate;
(meth)acrylic acid esters having a cyclic saturated hydrocarbon group, such as tricyclo[5.2.1.0 2,6 ]decan-8-yl(meth)acrylate;
(meth)acrylic acid esters having a cyclic unsaturated aliphatic hydrocarbon group, such as tricyclo[5.2.1.0 2,6 ]decene-8-yl (meth)acrylate;
Preferred are (meth)acrylic acid esters having an aromatic ring, such as benzyl (meth)acrylate and phenoxybenzyl (meth)acrylate.
　不飽和脂肪族炭化水素環を有するビニルモノマーとしては、ビシクロ［２．２．１］ヘプト－２－エン（または２－ノルボルネンともいう）、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、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類が挙げられる。
　不飽和複素環を有するビニルモノマーとしては、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、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類が挙げられる。
　芳香族環を有するビニルモノマーとしては、スチレン、α－メチルスチレン、ｍ－メチルスチレン、ｐ－メチルスチレン、ビニルトルエン、ｐ－メトキシスチレンなどのスチレン系モノマーが挙げられる。
　その他のビニルモノマーとして、アクリロニトリル、メタクリロニトリルなどのニトリル基含有モノマー；
　塩化ビニル、塩化ビニリデンなどのハロゲン原子含有モノマー；
　アクリルアミド、メタクリルアミド、酢酸ビニル、１，３－ブタジエン、イソプレン、２，３－ジメチル－１，３－ブタジエン等が挙げられる。
　これらのビニルモノマーのうち、共重合反応性及び耐熱性の点から、スチレン、ビニルトルエンなどのスチレン系モノマー、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などのジカルボニルイミド誘導体、ビシクロ［２．２．１］ヘプト－２－エン（または２－ノルボルネンともいう）等のビシクロ不飽和化合物が好ましい。 Examples of vinyl monomers having an unsaturated aliphatic hydrocarbon ring include bicyclo[2.2.1]hept-2-ene (also called 2-norbornene), 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'-hydroxy 5,6-di(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(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene are examples of bicyclo unsaturated compounds.
Examples of vinyl monomers having an unsaturated heterocycle include dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide.
Examples of vinyl monomers having an aromatic ring include styrene-based monomers such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene.
Other vinyl monomers include nitrile group-containing monomers such as acrylonitrile and methacrylonitrile;
Halogen atom-containing monomers such as vinyl chloride and vinylidene chloride;
Examples of the monomer include acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.
Among these vinyl monomers, from the viewpoints of copolymerization reactivity and heat resistance, styrene-based monomers such as styrene and vinyltoluene, dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide and N-benzylmaleimide, and bicyclo unsaturated compounds such as bicyclo[2.2.1]hept-2-ene (also called 2-norbornene) are preferred.
　（ａ）に由来する構造単位に（ｂ）を付加させた構造単位とは、共重合体の主鎖を構成する（ａ）由来の構造単位に付加によって（ｂ）が結合して構成される単位のことをいい、（ｂ）に由来するペンダント不飽和基を有する。この構造単位において、（ａ）は前記例示のいずれでもよく、（ｂ）も前記例示のいずれでもよい。（ａ）としては、（メタ）アクリル酸などの不飽和モノカルボン酸が好ましい。（ｂ）としては、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（ｂ１）が好ましく、直鎖状又は分枝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（ｂ１－１）がより好ましい。 The structural unit obtained by adding (b) to a structural unit derived from (a) refers to a unit formed by bonding (b) by addition to a structural unit derived from (a) constituting the main chain of the copolymer, and has a pendant unsaturated group derived from (b). In this structural unit, (a) may be any of the above-mentioned examples, and (b) may also be any of the above-mentioned examples. As (a), an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferable. As (b), a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond is preferable, and a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is more preferable.
　（ｂ）に由来する構造単位に（ａ）を付加させた構造単位とは、共重合体の主鎖を構成する（ｂ）由来の構造単位に付加によって（ａ）が結合して構成される単位のことをいい、（ａ）に由来するペンダント不飽和基を有する。この構造単位において、（ｂ）は前記例示のいずれでもよく、（ａ）も前記例示のいずれでもよい。（ｂ）としては、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（ｂ１）が好ましく、直鎖状又は分枝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（ｂ１－１）がより好ましい。（ａ）としては、（メタ）アクリル酸などの不飽和モノカルボン酸が好ましい。 The structural unit obtained by adding (a) to a structural unit derived from (b) refers to a unit formed by bonding (a) by addition to a structural unit derived from (b) constituting the main chain of the copolymer, and has a pendant unsaturated group derived from (a). In this structural unit, (b) may be any of the above-mentioned examples, and (a) may also be any of the above-mentioned examples. As (b), a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond is preferable, and a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is more preferable. As (a), an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferable.
　（ｂ）に由来する構造単位に（ａ）を付加させ、カルボン酸無水物をさらに付加させた構造単位とは、共重合体の主鎖を構成する（ｂ）由来の構造単位に付加によって（ａ）が結合して生じる水酸基に、カルボン酸無水物がハーフエステル化することによって結合した構造単位のことをいい、カルボン酸無水物に由来するペンダントカルボキシ基と、（ａ）に由来するペンダント不飽和基を有する。この構造単位において、（ｂ）は前記例示のいずれでもよく、（ａ）も前記例示のいずれでもよい。（ｂ）としては、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（ｂ１）が好ましく、直鎖状又は分枝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（ｂ１－１）がより好ましい。（ａ）としては、（メタ）アクリル酸などの不飽和モノカルボン酸が好ましい。
　カルボン酸無水物としては、マロン酸無水物、コハク酸無水物、グルタル酸無水物、アジピン酸無水物などの飽和脂肪族多価カルボン酸無水物；無水マレイン酸、シトラコン酸無水物、イタコン酸無水物などの不飽和脂肪族多価カルボン酸無水物；３－ビニルフタル酸無水物、４－ビニルフタル酸無水物などの芳香族多価カルボン酸無水物；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、５，６－ジカルボキシビシクロ［２．２．１］ヘプト－２－エン無水物などの脂環式多価カルボン酸無水物等の多価カルボン酸無水物が挙げられる。 The structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic anhydride refers to a structural unit obtained by half-esterification of a carboxylic anhydride to a hydroxyl group generated by adding (a) to a structural unit derived from (b) constituting the main chain of the copolymer, and has a pendant carboxyl group derived from the carboxylic anhydride and a pendant unsaturated group derived from (a). In this structural unit, (b) may be any of the above-mentioned examples, and (a) may also be any of the above-mentioned examples. As (b), a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond is preferable, and a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is more preferable. As (a), an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferable.
Examples of the carboxylic acid anhydride include saturated aliphatic polycarboxylic acid anhydrides such as malonic anhydride, succinic anhydride, glutaric anhydride, and adipic anhydride; unsaturated aliphatic polycarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, and itaconic anhydride; aromatic polycarboxylic acid anhydrides such as 3-vinylphthalic anhydride and 4-vinylphthalic anhydride; and alicyclic polycarboxylic acid anhydrides such as 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride.
　樹脂［Ｋ１］において、それぞれに由来する構造単位の比率は、樹脂［Ｋ１］を構成する全構造単位中、
（ａ）に由来する構造単位；２～６０モル％
（ｂ）に由来する構造単位；４０～９８モル％
であることが好ましく、
（ａ）に由来する構造単位；１０～５０モル％
（ｂ）に由来する構造単位；５０～９０モル％
であることがより好ましい。
　また（ｃ）に由来する構造単位は実質的に含まないことが好ましい。
　（ａ）に由来する構造単位と（ｂ）に由来する構造単位の合計は、樹脂［Ｋ１］を構成する全構造単位中、例えば、９０モル％以上、好ましくは９５モル％以上、より好ましくは９８モル％以上、特に好ましくは１００モル％である。
　樹脂［Ｋ１］の構造単位の比率が、上記の範囲にあると、着色硬化性樹脂組成物の保存安定性、着色パターンを形成する際の現像性、及び得られる光学フィルタの耐溶剤性に優れる傾向がある。 In the resin [K1], the ratio of the structural units derived from each of them to all the structural units constituting the resin [K1] is as follows:
Structural units derived from (a): 2 to 60 mol%
Structural units derived from (b): 40 to 98 mol%
It is preferred that
Structural units derived from (a): 10 to 50 mol %
Structural units derived from (b): 50 to 90 mol%
It is more preferable that:
It is also preferred that the copolymer is substantially free of structural units derived from (c).
The total of the structural units derived from (a) and the structural units derived from (b) is, for example, 90 mol % or more, preferably 95 mol % or more, more preferably 98 mol % or more, and particularly preferably 100 mol % of all the structural units constituting the resin [K1].
When the ratio of the structural units of the resin [K1] is within the above range, the colored curable resin composition tends to have excellent storage stability, developability when forming a colored pattern, and solvent resistance of the obtained optical filter.
　樹脂［Ｋ１］は、例えば、文献「高分子合成の実験法」（大津隆行著　発行所（株）化学同人　第１版第１刷　１９７２年３月１日発行）に記載された方法及び当該文献に記載された引用文献を参考にして製造することができる。 Resin [K1] can be produced, for example, by referring to the method described in the literature "Experimental Methods for Polymer Synthesis" (written by Otsu Takayuki, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, published March 1, 1972) and the references cited in said literature.
　具体的には、（ａ）及び（ｂ）の所定量、重合開始剤及び溶剤等を反応容器中に入れて、例えば、窒素により酸素を置換することにより、脱酸素雰囲気にし、攪拌しながら、加熱及び保温する方法が挙げられる。なお、ここで用いられる重合開始剤及び溶剤等は、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。例えば、重合開始剤としては、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、溶剤としては、各モノマーを溶解するものであればよく、本発明の着色硬化性樹脂組成物の溶剤（Ｅ）として後述する溶剤等が挙げられる。 Specific examples include a method in which predetermined amounts of (a) and (b), a polymerization initiator, a solvent, etc. are placed in a reaction vessel, and the atmosphere is deoxygenated, for example by replacing oxygen with nitrogen, and the mixture is heated and kept warm while stirring. The polymerization initiator and solvent used here are not particularly limited, and those commonly used in the field can be used. For example, polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.), and the solvent may be any that dissolves each monomer, such as the solvent (E) described below for the colored curable resin composition of the present invention.
　なお、得られた共重合体は、反応後の溶液をそのまま使用してもよいし、濃縮あるい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。特に、この重合の際に溶剤として、本発明の着色硬化性樹脂組成物に含まれる溶剤を使用することにより、反応後の溶液をそのまま本発明の着色硬化性樹脂組成物の調製に使用することができるため、本発明の着色硬化性樹脂組成物の製造工程を簡略化することができる。 The copolymer obtained may be used as it is in the solution after the reaction, or may be a concentrated or diluted solution, or may be extracted as a solid (powder) by a method such as reprecipitation. In particular, by using a solvent contained in the colored curable resin composition of the present invention as the solvent during this polymerization, the solution after the reaction can be used as it is in the preparation of the colored curable resin composition of the present invention, and the manufacturing process of the colored curable resin composition of the present invention can be simplified.
　樹脂［Ｋ２］において、それぞれに由来する構造単位の比率は、樹脂［Ｋ２］を構成する全構造単位中、
（ａ）に由来する構造単位；１～７０モル％
（ｂ）に由来する構造単位；１～６０モル％
（ｃ）に由来する構造単位；２０～９５モル％
であることが好ましく、
（ａ）に由来する構造単位；３～５０モル％
（ｂ）に由来する構造単位；３～４０モル％
（ｃ）に由来する構造単位；３０～９０モル％
であることがより好ましく、
（ａ）に由来する構造単位；５～４０モル％
（ｂ）に由来する構造単位；５～３０モル％
（ｃ）に由来する構造単位；４０～８０モル％
であることがよりさらに好ましい。
　（ａ）に由来する構造単位、（ｂ）に由来する構造単位、及び（ｃ）に由来する構造単位の合計は、樹脂［Ｋ２］を構成する全構造単位中、例えば、９０モル％以上、好ましくは９５モル％以上、より好ましくは９８モル％以上、特に好ましくは１００モル％である。
　樹脂［Ｋ２］の構造単位の比率が、上記の範囲にあると、着色硬化性樹脂組成物の保存安定性、着色パターンを形成する際の現像性、並びに、得られる光学フィルタの耐溶剤性、耐熱性及び機械強度に優れる傾向がある。 In the resin [K2], the ratio of the structural units derived from each of them to all the structural units constituting the resin [K2] is as follows:
Structural units derived from (a): 1 to 70 mol%
Structural units derived from (b): 1 to 60 mol%
Structural units derived from (c): 20 to 95 mol%
It is preferred that
Structural units derived from (a): 3 to 50 mol %
Structural units derived from (b): 3 to 40 mol%
Structural units derived from (c): 30 to 90 mol%
It is more preferable that
Structural units derived from (a): 5 to 40 mol%
Structural units derived from (b): 5 to 30 mol %
Structural units derived from (c): 40 to 80 mol%
It is even more preferred that:
The total of the structural units derived from (a), the structural units derived from (b), and the structural units derived from (c) is, for example, 90 mol % or more, preferably 95 mol % or more, more preferably 98 mol % or more, and particularly preferably 100 mol % of all the structural units constituting the resin [K2].
When the ratio of the structural units of the resin [K2] is within the above range, the colored curable resin composition tends to have excellent storage stability, developability when forming a colored pattern, and the obtained optical filter tends to have excellent solvent resistance, heat resistance, and mechanical strength.
　樹脂［Ｋ２］において（ａ）は（メタ）アクリル酸などの不飽和モノカルボン酸が好ましい。（ｂ）としては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（ｂ１）が好ましく、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（ｂ１－２）がより好ましい。（ｃ）としては、環状不飽和脂肪族炭化水素基を有する（メタ）アクリル酸エステル類、芳香族環を有する（メタ）アクリル酸エステル類、ジカルボニルイミド誘導体が好ましい。 In the resin [K2], (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid. As (b), a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond is preferred, and a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized is more preferred. As (c), (meth)acrylic acid esters having a cyclic unsaturated aliphatic hydrocarbon group, (meth)acrylic acid esters having an aromatic ring, and dicarbonyl imide derivatives are preferred.
　樹脂［Ｋ２］は、例えば、樹脂［Ｋ１］の製造方法として記載した方法と同様に製造することができる。 Resin [K2] can be produced, for example, in the same manner as described above for producing resin [K1].
　樹脂［Ｋ３］において、それぞれに由来する構造単位の比率は、樹脂［Ｋ３］を構成する全構造単位中、
（ａ）に由来する構造単位；２～６０モル％
（ｃ）に由来する構造単位；４０～９８モル％
であることが好ましく、
（ａ）に由来する構造単位；１０～５０モル％
（ｃ）に由来する構造単位；５０～９０モル％
であることがより好ましく、
（ａ）に由来する構造単位；３５～４５モル％
（ｃ）に由来する構造単位；５５～６５モル％
であることがよりさらに好ましい。
　また（ｂ）に由来する構造単位は実質的に含まないことが好ましい。
　（ａ）に由来する構造単位と（ｃ）に由来する構造単位の合計は、樹脂［Ｋ３］を構成する全構造単位中、例えば、９０モル％以上、好ましくは９５モル％以上、より好ましくは９８モル％以上、特に好ましくは１００モル％である。 In the resin [K3], the ratio of the structural units derived from each of them to all the structural units constituting the resin [K3] is as follows:
Structural units derived from (a): 2 to 60 mol%
Structural units derived from (c): 40 to 98 mol%
It is preferred that
Structural units derived from (a): 10 to 50 mol %
Structural units derived from (c): 50 to 90 mol%
It is more preferable that
Structural units derived from (a): 35 to 45 mol%
Structural units derived from (c): 55 to 65 mol%
It is even more preferred that:
It is also preferred that the copolymer is substantially free of structural units derived from (b).
The total of the structural units derived from (a) and the structural units derived from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% of all the structural units constituting the resin [K3].
　樹脂［Ｋ３］において（ａ）は（メタ）アクリル酸などの不飽和モノカルボン酸が好ましい。（ｃ）は芳香族環を有する（メタ）アクリル酸エステル類が好ましい。
　樹脂［Ｋ３］は、例えば、樹脂［Ｋ１］の製造方法として記載した方法と同様に製造することができる。 In the resin [K3], (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid, and (c) is preferably a (meth)acrylic acid ester having an aromatic ring.
Resin [K3] can be produced, for example, in the same manner as described above for producing resin [K1].
　樹脂［Ｋ４］において、それぞれに由来する構造単位の比率は、樹脂［Ｋ４］を構成する全構造単位中、
（ａ）に由来する構造単位（（ｂ）は付加していない）；１～６０モル％
（ａ）に由来する構造単位に（ｂ）を付加させた構造単位；１～５０モル％
（ｃ）に由来する構造単位；３０～９０モル％
であることが好ましく、
（ａ）に由来する構造単位（（ｂ）は付加していない）；５～５０モル％
（ａ）に由来する構造単位に（ｂ）を付加させた構造単位；５～４０モル％
（ｃ）に由来する構造単位；３５～８０モル％
であることがより好ましく、
（ａ）に由来する構造単位（（ｂ）は付加していない）；１０～４０モル％
（ａ）に由来する構造単位に（ｂ）を付加させた構造単位；１０～２５モル％
（ｃ）に由来する構造単位；４０～７５モル％
であることがよりさらに好ましい。
　（ａ）に由来する構造単位（（ｂ）は付加していない）と、（ａ）に由来する構造単位に（ｂ）を付加させた構造単位と、（ｃ）に由来する構造単位の合計は、樹脂［Ｋ４］を構成する全構造単位中、例えば、９０モル％以上、好ましくは９５モル％以上、より好ましくは９８モル％以上、特に好ましくは１００モル％である。 In the resin [K4], the ratio of the structural units derived from each of them to all the structural units constituting the resin [K4] is as follows:
Structural units derived from (a) (without (b) added): 1 to 60 mol%
Structural units obtained by adding (b) to a structural unit derived from (a): 1 to 50 mol %
Structural units derived from (c): 30 to 90 mol%
It is preferred that
Structural units derived from (a) (without (b) added): 5 to 50 mol %
Structural units obtained by adding (b) to a structural unit derived from (a): 5 to 40 mol%
Structural units derived from (c): 35 to 80 mol%
It is more preferable that
Structural units derived from (a) (without (b) added): 10 to 40 mol%
Structural units obtained by adding (b) to a structural unit derived from (a): 10 to 25 mol%
Structural units derived from (c): 40 to 75 mol%
It is even more preferred that:
The total of the structural units derived from (a) (to which (b) is not added), the structural units obtained by adding (b) to the structural units derived from (a), and the structural units derived from (c) is, for example, 90 mol % or more, preferably 95 mol % or more, more preferably 98 mol % or more, and particularly preferably 100 mol % of all the structural units constituting the resin [K4].
　（ａ）に由来する構造単位（（ｂ）は付加していない）としては、（メタ）アクリル酸などの不飽和モノカルボン酸に由来する構造単位が好ましい。（ａ）に由来する構造単位に（ｂ）を付加させた構造単位としては、（メタ）アクリル酸などの不飽和モノカルボン酸に由来する構造単位に、直鎖状又は分枝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（ｂ１－１）を付加させた構造単位が好ましい。（ｃ）に由来する構造単位としては、直鎖又は分岐鎖の脂肪族飽和炭化水素基を有する（メタ）アクリル酸エステル類、環状飽和炭化水素基を有する（メタ）アクリル酸エステル類、芳香族環を有する（メタ）アクリル酸エステル類、ビシクロ不飽和化合物、及びスチレン系モノマーから選ばれる１種以上が好ましく、２種以上がより好ましい。（ｃ）に由来する構成単位を２種有する場合の（ｃ）は、（メタ）アクリル酸エステル類、環状飽和炭化水素基を有する（メタ）アクリル酸エステル類、芳香族環を有する（メタ）アクリル酸エステル類などの不飽和カルボン酸エステル類から２種を選択し、ビシクロ不飽和化合物、及びスチレン系モノマーなどのビニルモノマーから選ばれる２種以上を選択することが好ましい。 As the structural unit derived from (a) (without the addition of (b)), a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred. As the structural unit in which (b) is added to a structural unit derived from (a), a structural unit in which a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is added to a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred. As the structural unit derived from (c), one or more types selected from (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group, (meth)acrylic acid esters having a cyclic saturated hydrocarbon group, (meth)acrylic acid esters having an aromatic ring, bicyclo unsaturated compounds, and styrene-based monomers are preferred, and two or more types are more preferred. When (c) has two types of structural units derived from it, it is preferable to select two types from unsaturated carboxylic acid esters such as (meth)acrylic acid esters, (meth)acrylic acid esters having a cyclic saturated hydrocarbon group, and (meth)acrylic acid esters having an aromatic ring, and to select two or more types from bicyclo unsaturated compounds and vinyl monomers such as styrene-based monomers.
　樹脂［Ｋ４］は、（ａ）と（ｃ）との共重合体を得て、（ｂ）が有する炭素数２～４の環状エーテルを（ａ）が有するカルボン酸及び／又はカルボン酸無水物に付加させることにより製造することができる。
　まず（ａ）と（ｃ）との共重合体を、樹脂［Ｋ１］の製造方法として記載した方法と同様に製造する。この場合、それぞれに由来する構造単位の比率は、樹脂［Ｋ３］で挙げたもの同じ比率であることが好ましい。 Resin [K4] can be produced by obtaining a copolymer of (a) and (c), and adding the cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and/or carboxylic acid anhydride contained in (a).
First, a copolymer of (a) and (c) is produced in the same manner as described for the production method of resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same as that described for resin [K3].
　次に、前記共重合体中の（ａ）に由来するカルボン酸及び／又はカルボン酸無水物の一部に、（ｂ）が有する炭素数２～４の環状エーテルを反応させる。
　（ａ）と（ｃ）との共重合体の製造に引き続き、フラスコ内雰囲気を窒素から空気に置換し、（ｂ）、カルボン酸又はカルボン酸無水物と環状エーテルとの反応触媒（例えばトリス（ジメチルアミノメチル）フェノール等）及び重合禁止剤（例えばハイドロキノン等）等をフラスコ内に入れて、例えば、６０～１３０℃で、１～１０時間反応することにより、樹脂［Ｋ４］を製造することができる。
　（ｂ）の使用量は、（ａ）１００モルに対して、５～８０モルが好ましく、より好ましくは１０～７５モルである。この範囲にすることにより、着色硬化性樹脂組成物の保存安定性、パターンを形成する際の現像性、並びに、得られるパターンの耐溶剤性、耐熱性、機械強度及び感度のバランスが良好になる傾向がある。
　前記反応触媒の使用量は、（ａ）、（ｂ）及び（ｃ）の合計量１００質量部に対して０．００１～５質量部が好ましい。前記重合禁止剤の使用量は、（ａ）、（ｂ）及び（ｃ）の合計量１００質量部に対して０．００１～５質量部が好ましい。
　仕込方法、反応温度及び時間等の反応条件は、製造設備や重合による発熱量等を考慮して適宜調整することができる。なお、重合条件と同様に、製造設備や重合による発熱量等を考慮し、仕込方法や反応温度を適宜調整することができる。 Next, a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms contained in (b).
Following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air from nitrogen, and (b) a catalyst for the reaction of a carboxylic acid or a carboxylic acid anhydride with a cyclic ether (e.g., tris(dimethylaminomethyl)phenol, etc.), a polymerization inhibitor (e.g., hydroquinone, etc.), etc. are placed in the flask, and the mixture is reacted, for example, at 60 to 130° C. for 1 to 10 hours, thereby producing the resin [K4].
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, relative to 100 mol of (a). By using this range, the storage stability of the colored curable resin composition, the developability when forming a pattern, and the balance of the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern tend to be good.
The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c).The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c).
The reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, etc. As with the polymerization conditions, the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, etc.
　樹脂［Ｋ４’］において、それぞれに由来する構造単位の比率は、樹脂［Ｋ４’］を構成する全構造単位中、
（ａ）に由来する構造単位に（ｂ）を付加させた構造単位；５～９５モル％
（ｃ）に由来する構造単位；５～９５モル％
であることが好ましく、
（ａ）に由来する構造単位に（ｂ）を付加させた構造単位；１５～９０モル％
（ｃ）に由来する構造単位；１０～８５モル％
であることがより好ましく、
（ａ）に由来する構造単位に（ｂ）を付加させた構造単位；２０～８０モル％
（ｃ）に由来する構造単位；２０～８０モル％
であることがよりさらに好ましい。
　また（ａ）に由来する構造単位であって（ｂ）が付加していないものは実質的に含まない。
　（ａ）に由来する構造単位に（ｂ）を付加させた構造単位と、（ｃ）に由来する構造単位の合計は、樹脂［Ｋ５’］を構成する全構造単位中、例えば、９０モル％以上、好ましくは９５モル％以上、より好ましくは９８モル％以上、特に好ましくは１００モル％である。 In the resin [K4'], the ratio of the structural units derived from each of them to all the structural units constituting the resin [K4'] is as follows:
Structural units obtained by adding (b) to a structural unit derived from (a): 5 to 95 mol%
Structural units derived from (c): 5 to 95 mol%
It is preferred that
Structural units obtained by adding (b) to a structural unit derived from (a): 15 to 90 mol%
Structural units derived from (c): 10 to 85 mol%
It is more preferable that
Structural units obtained by adding (b) to a structural unit derived from (a): 20 to 80 mol%
Structural units derived from (c): 20 to 80 mol%
It is even more preferred that:
Furthermore, structural units derived from (a) to which (b) has not been added are substantially not included.
The sum of the structural unit obtained by adding (b) to the structural unit derived from (a) and the structural unit derived from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% of all structural units constituting the resin [K5'].
　（ａ）に由来する構造単位に（ｂ）を付加させた構造単位としては、（メタ）アクリル酸などの不飽和モノカルボン酸に由来する構造単位に、直鎖状又は分枝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（ｂ１－１）を付加させた構造単位が好ましい。（ｃ）に由来する構造単位としては、直鎖又は分岐鎖の脂肪族飽和炭化水素基を有する（メタ）アクリル酸エステル類、環状飽和炭化水素基を有する（メタ）アクリル酸エステル類から選ばれる１種以上が好ましく、２種以上がより好ましい。
　樹脂［Ｋ４’］は、上記の樹脂［Ｋ４］の製造方法を参照して行ってもよく、（ｂ）の使用量は、（ａ）１００モルに対して、１００モルであることが好ましい。 The structural unit obtained by adding (b) to a structural unit derived from (a) is preferably a structural unit obtained by adding a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized to a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid. The structural unit derived from (c) is preferably one or more selected from (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group and (meth)acrylic acid esters having a cyclic saturated hydrocarbon group, more preferably two or more.
Resin [K4'] may be produced by referring to the production method of resin [K4] described above, and the amount of (b) used is preferably 100 mol per 100 mol of (a).
　樹脂［Ｋ５］において、それぞれに由来する構造単位の比率は、樹脂［Ｋ５］を構成する全構造単位中、
（ｂ）に由来する構造単位（（ａ）は付加していない）；０～３０モル％
（ｂ）に由来する構造単位に（ａ）を付加させた構造単位；５～９５モル％
（ｃ）に由来する構造単位；５～９５モル％
であることが好ましく、
（ｂ）に由来する構造単位（（ａ）は付加していない）；０～１０モル％
（ｂ）に由来する構造単位に（ａ）を付加させた構造単位；１５～９０モル％
（ｃ）に由来する構造単位；１０～８５モル％
であることがより好ましく、
（ｂ）に由来する構造単位（（ａ）は付加していない）；０～５モル％
（ｂ）に由来する構造単位に（ａ）を付加させた構造単位；２０～８０モル％
（ｃ）に由来する構造単位；２０～８０モル％
であることがよりさらに好ましい。
　（ｂ）に由来する構造単位（（ａ）は付加していない）と、（ｂ）に由来する構造単位に（ａ）を付加させた構造単位と、（ｃ）に由来する構造単位の合計は、樹脂［Ｋ５］を構成する全構造単位中、例えば、９０モル％以上、好ましくは９５モル％以上、より好ましくは９８モル％以上、特に好ましくは１００モル％である。 In the resin [K5], the ratio of the structural units derived from each of them to all the structural units constituting the resin [K5] is as follows:
Structural units derived from (b) ((a) is not added): 0 to 30 mol%
Structural units obtained by adding (a) to a structural unit derived from (b): 5 to 95 mol%
Structural units derived from (c): 5 to 95 mol%
It is preferred that
Structural units derived from (b) ((a) is not added): 0 to 10 mol%
Structural units obtained by adding (a) to a structural unit derived from (b): 15 to 90 mol%
Structural units derived from (c): 10 to 85 mol%
It is more preferable that
Structural units derived from (b) ((a) is not added): 0 to 5 mol%
Structural units obtained by adding (a) to a structural unit derived from (b): 20 to 80 mol%
Structural units derived from (c): 20 to 80 mol%
It is even more preferred that:
The total of the structural units derived from (b) (to which (a) is not added), the structural units obtained by adding (a) to the structural units derived from (b), and the structural units derived from (c) is, for example, 90 mol % or more, preferably 95 mol % or more, more preferably 98 mol % or more, and particularly preferably 100 mol % of all the structural units constituting the resin [K5].
　（ｂ）に由来する構造単位（（ａ）は付加していない）としては、直鎖状又は分枝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（ｂ１－１）に由来する構造単位が好ましい。（ｂ）に由来する構造単位に（ａ）を付加させた構造単位としては、直鎖状又は分枝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（ｂ１－１）に由来する構造単位に（メタ）アクリル酸などの不飽和モノカルボン酸を付加させた構造単位が好ましい。（ｃ）に由来する構造単位としては、直鎖又は分岐鎖の脂肪族飽和炭化水素基を有する（メタ）アクリル酸エステル類、環状飽和炭化水素基を有する（メタ）アクリル酸エステル類から選ばれる１種以上が好ましく、２種以上がより好ましい。 As the structural unit derived from (b) (without (a) added), a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is preferred. As the structural unit in which (a) is added to a structural unit derived from (b), a structural unit in which an unsaturated monocarboxylic acid such as (meth)acrylic acid is added to a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is preferred. As the structural unit derived from (c), one or more types selected from (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group and (meth)acrylic acid esters having a cyclic saturated hydrocarbon group are preferred, and two or more types are more preferred.
　樹脂［Ｋ５］は、第一段階として、上述した樹脂［Ｋ１］の製造方法と同様にして、（ｂ）と（ｃ）との共重合体を得る。上記と同様に、得られた共重合体は、反応後の溶液をそのまま使用してもよいし、濃縮あるい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。
　（ｂ）及び（ｃ）に由来する構造単位の比率は、前記の共重合体を構成する全構造単位の合計モル数に対して、それぞれ、
（ｂ）に由来する構造単位；５～９５モル％
（ｃ）に由来する構造単位；５～９５モル％
であることが好ましく、
（ｂ）に由来する構造単位；１０～９０モル％
（ｃ）に由来する構造単位；１０～９０モル％
であることがより好ましい。 Resin [K5] is produced in the first step by the same method as that for producing resin [K1] described above, to obtain a copolymer of (b) and (c). As in the above, the copolymer obtained may be used as it is in the form of a solution after the reaction, or may be a concentrated or diluted solution, or may be extracted as a solid (powder) by a method such as reprecipitation.
The ratios of the structural units derived from (b) and (c) to the total number of moles of all structural units constituting the copolymer are, respectively,
Structural units derived from (b): 5 to 95 mol%
Structural units derived from (c): 5 to 95 mol%
It is preferred that
Structural units derived from (b): 10 to 90 mol%
Structural units derived from (c): 10 to 90 mol%
It is more preferable that:
　さらに、樹脂［Ｋ４］又は樹脂［Ｋ４’］の製造方法と同様の条件で、（ｂ）と（ｃ）との共重合体が有する（ｂ）に由来する環状エーテルに、（ａ）が有するカルボン酸又はカルボン酸無水物を反応させることにより、樹脂［Ｋ５］を得ることができる。
　前記の共重合体に反応させる（ａ）の使用量は、（ｂ）１００モルに対して、５～１００モルが好ましい。環状エーテルの反応性が高く、未反応の（ｂ）が残存しにくいことから、樹脂［Ｋ５］に用いる（ｂ）としては（ｂ１）が好ましく、さらに（ｂ１－１）が好ましい。 Furthermore, under the same conditions as in the production method of resin [K4] or resin [K4'], resin [K5] can be obtained by reacting a cyclic ether derived from (b) contained in a copolymer of (b) and (c) with a carboxylic acid or carboxylic acid anhydride contained in (a).
The amount of (a) to be reacted with the copolymer is preferably 5 to 100 moles per 100 moles of (b). Because the reactivity of cyclic ethers is high and unreacted (b) is unlikely to remain, (b1) is preferred as (b) for use in resin [K5], and (b1-1) is more preferred.
　樹脂［Ｋ６］において、それぞれに由来する構造単位の比率は、樹脂［Ｋ６］を構成する全構造単位中、
（ｂ）に由来する構造単位（（ａ）は付加していない）；０～３０モル％
（ｂ）に由来する構造単位に（ａ）を付加させた構造単位（カルボン酸無水物は付加していない）；２０～８５モル％
（ｂ）に由来する構造単位に（ａ）を付加させ、カルボン酸無水物をさらに付加させた構造単位；２～４０モル％
（ｃ）に由来する構造単位；１０～６０モル％
であることが好ましく、
（ｂ）に由来する構造単位（（ａ）は付加していない）；０～１０モル％
（ｂ）に由来する構造単位に（ａ）を付加させた構造単位（カルボン酸無水物は付加していない）；４０～８０モル％
（ｂ）に由来する構造単位に（ａ）を付加させ、カルボン酸無水物をさらに付加させた構造単位；３～３０モル％
（ｃ）に由来する構造単位；１５～５０モル％
であることがより好ましく、
（ｂ）に由来する構造単位（（ａ）は付加していない）；０～５モル％
（ｂ）に由来する構造単位に（ａ）を付加させた構造単位（カルボン酸無水物は付加していない）；５０～７０モル％
（ｂ）に由来する構造単位に（ａ）を付加させ、カルボン酸無水物をさらに付加させた構造単位；５～２０モル％
（ｃ）に由来する構造単位；２０～４０モル％
であることがよりさらに好ましい。 In the resin [K6], the ratio of the structural units derived from each of them to all the structural units constituting the resin [K6] is as follows:
Structural units derived from (b) ((a) is not added): 0 to 30 mol%
Structural units in which (a) is added to a structural unit derived from (b) (no carboxylic anhydride is added): 20 to 85 mol%
A structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic acid anhydride thereto: 2 to 40 mol %
Structural units derived from (c): 10 to 60 mol%
It is preferred that
Structural units derived from (b) ((a) is not added): 0 to 10 mol%
Structural units in which (a) is added to a structural unit derived from (b) (no carboxylic anhydride is added): 40 to 80 mol%
A structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic acid anhydride thereto: 3 to 30 mol %
Structural units derived from (c): 15 to 50 mol%
It is more preferable that
Structural units derived from (b) ((a) is not added): 0 to 5 mol%
A structural unit obtained by adding (a) to a structural unit derived from (b) (no carboxylic acid anhydride is added); 50 to 70 mol%
A structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic acid anhydride thereto: 5 to 20 mol %
Structural units derived from (c): 20 to 40 mol%
It is even more preferred that:
　（ｂ）に由来する構造単位（（ａ）は付加していない）と、（ｂ）に由来する構造単位に（ａ）を付加させた構造単位（カルボン酸無水物は付加していない）と、（ｂ）に由来する構造単位に（ａ）を付加させ、カルボン酸無水物をさらに付加させた構造単位と、（ｃ）に由来する構造単位の合計は、樹脂［Ｋ６］を構成する全構造単位中、例えば、９０モル％以上、好ましくは９５モル％以上、より好ましくは９８モル％以上、特に好ましくは１００モル％である。 The total of the structural units derived from (b) (without (a) added), the structural units in which (a) is added to the structural units derived from (b) (without carboxylic anhydride added), the structural units in which (a) is added to the structural units derived from (b) and a carboxylic anhydride is further added, and the structural units derived from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% of all the structural units constituting the resin [K6].
　（ｂ）に由来する構造単位（（ａ）は付加していない）としては、直鎖状又は分枝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（ｂ１－１）に由来する構造単位が好ましい。（ｂ）に由来する構造単位に（ａ）を付加させた構造単位（カルボン酸無水物は付加していない）としては、直鎖状又は分枝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（ｂ１－１）に由来する構造単位に（メタ）アクリル酸などの不飽和モノカルボン酸を付加させた構造単位が好ましい。（ｂ）に由来する構造単位に（ａ）を付加させ、カルボン酸無水物をさらに付加させた構造単位としては、直鎖状又は分枝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（ｂ１－１）に由来する構造単位に（メタ）アクリル酸などの不飽和モノカルボン酸を付加させ、無水コハク酸などの飽和脂肪族多価カルボン酸無水物をさらに付加させた構造単位が好ましい。（ｃ）に由来する構造単位としては、直鎖又は分岐鎖の脂肪族飽和炭化水素基を有する（メタ）アクリル酸エステル類、環状飽和炭化水素基を有する（メタ）アクリル酸エステル類から選ばれる１種以上が好ましく、２種以上がより好ましい。 As the structural unit derived from (b) (without (a) added), a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is preferred. As the structural unit in which (a) is added to a structural unit derived from (b) (without carboxylic anhydride added), a structural unit in which an unsaturated monocarboxylic acid such as (meth)acrylic acid is added to a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is preferred. As the structural unit in which (a) is added to a structural unit derived from (b) and a carboxylic anhydride is further added, a structural unit in which an unsaturated monocarboxylic acid such as (meth)acrylic acid is added to a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized and a saturated aliphatic polycarboxylic anhydride such as succinic anhydride is further added. As the structural unit derived from (c), one or more types selected from (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group and (meth)acrylic acid esters having a cyclic saturated hydrocarbon group are preferred, and two or more types are more preferred.
　樹脂［Ｋ６］は、第一段階として、上述した樹脂［Ｋ１］の製造方法と同様にして、（ｂ）と（ｃ）との共重合体を得る。上記と同様に、得られた共重合体は、反応後の溶液をそのまま使用してもよいし、濃縮あるい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。
　（ｂ）及び（ｃ）に由来する構造単位の比率は、前記の共重合体を構成する全構造単位の合計モル数に対して、それぞれ、
（ｂ）に由来する構造単位；５～９５モル％
（ｃ）に由来する構造単位；５～９５モル％
であることが好ましく、
（ｂ）に由来する構造単位；１０～９０モル％
（ｃ）に由来する構造単位；１０～９０モル％
であることがより好ましい。 Resin [K6] is produced in the first step by the same method as that for producing resin [K1] described above, to obtain a copolymer of (b) and (c). As in the above, the copolymer obtained may be used as it is in the form of a solution after the reaction, or a concentrated or diluted solution, or may be extracted as a solid (powder) by a method such as reprecipitation.
The ratios of the structural units derived from (b) and (c) to the total number of moles of all structural units constituting the copolymer are, respectively,
Structural units derived from (b): 5 to 95 mol%
Structural units derived from (c): 5 to 95 mol%
It is preferred that
Structural units derived from (b): 10 to 90 mol%
Structural units derived from (c): 10 to 90 mol%
It is more preferable that:
　さらに、樹脂［Ｋ４］の製造方法と同様の条件で、（ｂ）と（ｃ）との共重合体が有する（ｂ）に由来する環状エーテルに、（ａ）が有するカルボン酸又はカルボン酸無水物を反応させる。（ａ）の使用量は、（ｂ）１００モルに対して、８０～１００モルが好ましい。 Furthermore, under the same conditions as in the manufacturing method of resin [K4], the cyclic ether derived from (b) contained in the copolymer of (b) and (c) is reacted with the carboxylic acid or carboxylic anhydride contained in (a). The amount of (a) used is preferably 80 to 100 moles per 100 moles of (b).
　前記環状エーテルと（ａ）が有するカルボン酸又はカルボン酸無水物との反応により発生するヒドロキシ基に、カルボン酸無水物を反応させる。
　カルボン酸無水物の使用量は、（ａ）の使用量１モル（言い換えれば（ａ）の使用によって生じたヒドロキシ基１モル）に対して、０．０５～１モルが好ましく、０．１０～０．８モルがより好ましく、０．１３～０．７モルがよりさらに好ましい。 The hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or carboxylic acid anhydride contained in (a) is reacted with the carboxylic acid anhydride.
The amount of the carboxylic acid anhydride used is preferably 0.05 to 1 mol, more preferably 0.10 to 0.8 mol, and even more preferably 0.13 to 0.7 mol, relative to 1 mol of the amount of (a) used (in other words, 1 mol of hydroxy groups generated by the use of (a)).
　樹脂（Ｂ）としては、具体的に、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］デシルアクリレート／（メタ）アクリル酸共重合体等の樹脂［Ｋ１］；
　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／トリシクロ［５．２．１．０2,6］デセン－８－イル（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］デシルアクリレート／（メタ）アクリル酸／ベンジル（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］デシルアクリレート／（メタ）アクリル酸／フェノキシベンジル（メタ）アクリレート共重合体、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／スチレン共重合体等の樹脂［Ｋ２］；
　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等の樹脂［Ｋ３］；
　ベンジル（メタ）アクリレート／（メタ）アクリル酸共重合体のカルボン酸基の一部にグリシジル（メタ）アクリレートを付加させた樹脂、トリシクロデシル（メタ）アクリレート／スチレン／（メタ）アクリル酸共重合体のカルボン酸基の一部にグリシジル（メタ）アクリレートを付加させた樹脂、トリシクロデシル（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のカルボン酸基の一部にグリシジル（メタ）アクリレートを付加させた樹脂、ノルボルネン／ビニルトルエン／（メタ）アクリル酸共重合体のカルボン酸基の一部にグリシジル（メタ）アクリレートを付加させた樹脂、ノルボルネン／スチレン／（メタ）アクリル酸共重合体のカルボン酸基の一部にグリシジル（メタ）アクリレートを付加させた樹脂等の樹脂［Ｋ４］；
　トリシクロデシル（メタ）アクリレート／（メタ）アクリル酸の共重合体にグリシジル（メタ）アクリレートを反応させた樹脂、トリシクロデシル（メタ）アクリレート／スチレン／（メタ）アクリル酸の共重合体にグリシジル（メタ）アクリレートを反応させた樹脂等の樹脂［Ｋ４’］；
　トリシクロデシル（メタ）アクリレート／グリシジル（メタ）アクリレートの共重合体に（メタ）アクリル酸を反応させた樹脂、トリシクロデシル（メタ）アクリレート／スチレン／グリシジル（メタ）アクリレートの共重合体に（メタ）アクリル酸を反応させた樹脂等の樹脂［Ｋ５］；
　トリシクロデシル（メタ）アクリレート／グリシジル（メタ）アクリレートの共重合体に（メタ）アクリル酸を反応させた樹脂にさらにテトラヒドロフタル酸無水物を反応させた樹脂、２－エチルヘキシル（メタ）アクリレート／トリシクロデシル（メタ）アクリレート／グリシジル（メタ）アクリレートの共重合体に（メタ）アクリル酸を反応させた樹脂にさらに無水コハク酸を反応させた樹脂、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／トリシクロデシル（メタ）アクリレート／グリシジル（メタ）アクリレートの共重合体に（メタ）アクリル酸を反応させた樹脂にさらに無水コハク酸を反応させた樹脂等の樹脂［Ｋ６］等が挙げられる。 Specific examples of the resin (B) include resins [K1] such as 3,4-epoxycyclohexylmethyl(meth)acrylate/(meth)acrylic acid copolymer and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate/(meth)acrylic acid copolymer;
Glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide/tricyclo[5.2.1.0 2,6 ] decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide/tricyclo[5.2.1.0 2,6 ] decene-8-yl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] decyl acrylate/(meth)acrylic acid/benzyl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] Decyl acrylate/(meth)acrylic acid/phenoxybenzyl (meth)acrylate copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer, and other resins [K2];
Resins such as benzyl (meth)acrylate/(meth)acrylic acid copolymers and styrene/(meth)acrylic acid copolymers [K3];
Resins [K4] such as a resin in which glycidyl (meth)acrylate is added to a portion of the carboxylic acid groups of a benzyl (meth)acrylate/(meth)acrylic acid copolymer, a resin in which glycidyl (meth)acrylate is added to a portion of the carboxylic acid groups of a tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, a resin in which glycidyl (meth)acrylate is added to a portion of the carboxylic acid groups of a tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, a resin in which glycidyl (meth)acrylate is added to a portion of the carboxylic acid groups of a norbornene/vinyl toluene/(meth)acrylic acid copolymer, and a resin in which glycidyl (meth)acrylate is added to a portion of the carboxylic acid groups of a norbornene/styrene/(meth)acrylic acid copolymer;
Resins [K4'] such as a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/(meth)acrylic acid with glycidyl (meth)acrylate, and a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid with glycidyl (meth)acrylate;
Resins [K5] such as a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid, and a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate with (meth)acrylic acid;
Examples of the resin [K6] include a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid and further reacting the resulting resin with tetrahydrophthalic anhydride, a resin obtained by reacting a copolymer of 2-ethylhexyl (meth)acrylate/tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid and further reacting the resulting resin with succinic anhydride, and a resin obtained by reacting a copolymer of methyl (meth)acrylate/2-ethylhexyl (meth)acrylate/tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid and further reacting the resulting resin with succinic anhydride.
　樹脂［Ｋ１］～［Ｋ６］は、１種でもよく２種以上を組み合わせてもよい。好ましい組み合わせには、例えば、樹脂［Ｋ２］と［Ｋ６］の組み合わせが含まれる。樹脂［Ｋ２］と［Ｋ６］を組み合わせる場合、樹脂［Ｋ２］は、樹脂［Ｋ２］と樹脂［Ｋ６］の合計１００質量部に対して、例えば、１～５０質量部、好ましくは５～４０質量部、より好ましくは１０～３０質量部である。 Resins [K1] to [K6] may be of one type or of a combination of two or more types. A preferred combination includes, for example, a combination of resins [K2] and [K6]. When resins [K2] and [K6] are combined, the amount of resin [K2] is, for example, 1 to 50 parts by mass, preferably 5 to 40 parts by mass, and more preferably 10 to 30 parts by mass, per 100 parts by mass of the total of resins [K2] and [K6].
　樹脂（Ｂ）のポリスチレン換算の重量平均分子量は、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。分子量が前記の範囲内にあると、光学フィルタの硬度が向上し、残膜率が高く、未露光部の現像液に対する溶解性が良好で、着色パターンの解像度が向上する傾向がある。
　樹脂（Ｂ）の分散度［重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ）］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。 The polystyrene-equivalent weight average molecular weight of resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the optical filter is improved, the residual film rate is high, the solubility of the unexposed portion in the developer is good, and the resolution of the colored pattern tends to be improved.
The polydispersity of the resin (B) [weight average molecular weight (Mw)/number average molecular weight (Mn)] is preferably 1.1-6, and more preferably 1.2-4.
　樹脂（Ｂ）の酸価は、固形分換算で、好ましくは２０～１７０ｍｇ－ＫＯＨ／ｇであり、より好ましくは２５～１５０ｍｇ－ＫＯＨ／ｇ、さらに好ましくは３０～１３５ｍｇ－ＫＯＨ／ｇである。ここで酸価は樹脂（Ｂ）１ｇを中和するために必要な水酸化カリウムの量（ｍｇ）として測定される値であり、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 of resin (B) is preferably 20 to 170 mg-KOH/g, more preferably 25 to 150 mg-KOH/g, and even more preferably 30 to 135 mg-KOH/g, calculated as solid content. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin (B), and can be determined, for example, by titration with an aqueous potassium hydroxide solution.
　樹脂（Ｂ）の含有率は、固形分の総量に対して、好ましくは２～６５質量％であり、より好ましくは３～６０質量％であり、さらに好ましくは５～５５質量％である。樹脂（Ｂ）の含有率が、前記の範囲内にあると、着色パターンが形成でき、また着色パターンの解像度及び残膜率が向上する傾向がある。 The content of resin (B) is preferably 2 to 65 mass % relative to the total amount of solids, more preferably 3 to 60 mass %, and even more preferably 5 to 55 mass %. When the content of resin (B) is within the above range, a colored pattern can be formed, and the resolution and remaining film rate of the colored pattern tend to improve.
＜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及び／又は酸によって重合しうる化合物であり、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、好ましくは（メタ）アクリル酸エステル化合物である。 <Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by the active radicals and/or acids generated from the polymerization initiator (D). For example, a compound having a polymerizable ethylenically unsaturated bond can be mentioned. is a (meth)acrylic acid ester compound.
　エチレン性不飽和結合を１つ有する重合性化合物としては、例えば、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、並びに、上述の単量体（ａ）、単量体（ｂ）及び単量体（ｃ）等が挙げられる。 Examples of polymerizable compounds having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the above-mentioned monomers (a), (b), and (c).
　エチレン性不飽和結合を２つ有する重合性化合物としては、例えば、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）エーテル及び３－メチルペンタンジオールジ（メタ）アクリレート等が挙げられる。 Examples of polymerizable compounds having two ethylenically unsaturated bonds include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl)ether of bisphenol A, and 3-methylpentanediol di(meth)acrylate.
　中でも、重合性化合物（Ｃ）は、エチレン性不飽和結合を３つ以上有する重合性化合物であることが好ましい。このような重合性化合物としては、例えば、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ポリ（メタ）アクリレート（例えば、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート）、ジペンタエリスリトールポリ（メタ）アクリレート（例えば、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート）、トリペンタエリスリトールポリ（メタ）アクリレート（例えば、トリペンタエリスリトールオクタ（メタ）アクリレート、トリペンタエリスリトールヘプタ（メタ）アクリレート）、テトラペンタエリスリトールポリ（メタ）アクリレート（例えば、テトラペンタエリスリトールデカ（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）、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、アルコキシ化ペンタエリスリトールポリ（メタ）アクリレート（例えば、エトキシ化ペンタエリスリトールトリ（メタ）アクリレート、エトキシ化ペンタエリスリトールテトラ（メタ）アクリレート、プロポキシ化ペンタエリスリトールトリ（メタ）アクリレート、プロポキシ化ペンタエリスリトールテトラ（メタ）アクリレート）、アルコキシ化ジペンタエリスリトールポリ（メタ）アクリレート（例えば、エトキシ化ジペンタエリスリトールペンタ（メタ）アクリレート、エトキシ化ジペンタエリスリトールヘキサ（メタ）アクリレート、プロポキシ化ジペンタエリスリトールペンタ（メタ）アクリレート、プロポキシ化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ペンタエリスリトールポリ（メタ）アクリレート（例えば、カプロラクトン変性ペンタエリスリトールトリ（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）、カプロラクトン変性ジペンタエリスリトールポリ（メタ）アクリレート（例えば、カプロラクトン変性ジペンタエリスリトールペンタ（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）等が挙げられる。
　中でも、トリメチロールプロパントリ（メタ）アクリレート及びジペンタエリスリトールポリ（メタ）アクリレートからなる群から選択される少なくとも１種を含むことが好ましく、トリメチロールプロパントリアクリレート及びジペンタエリスリトールポリアクリレートからなる群から選択される少なくとも１種を含むことがより好ましい。 Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol poly(meth)acrylate (e.g., pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate), dipentaerythritol poly(meth)acrylate (e.g., dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate), tripentaerythritol poly(meth)acrylate (e.g., tri(meth)acrylate ... pentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate), tetrapentaerythritol poly(meth)acrylate (e.g., tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate), tris(2-(meth)acryloyloxyethyl)isocyanurate, alkoxylated pentaerythritol poly(meth)acrylate (e.g., ethoxylated pentaerythritol tri(meth)acrylate, ethoxylated alkoxylated pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate), alkoxylated dipentaerythritol poly(meth)acrylates (e.g., ethoxylated dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol penta(meth)acrylate, propoxylated dipentaerythritol caprolactone-modified pentaerythritol poly(meth)acrylates (e.g., caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate), caprolactone-modified dipentaerythritol poly(meth)acrylates (e.g., caprolactone-modified dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate).
Among these, it is preferable to include at least one selected from the group consisting of trimethylolpropane tri(meth)acrylate and dipentaerythritol poly(meth)acrylate, and it is more preferable to include at least one selected from the group consisting of trimethylolpropane triacrylate and dipentaerythritol polyacrylate.
　重合性化合物（Ｃ）の重量平均分子量は、好ましくは５０以上４，０００以下であり、より好ましくは７０以上３，５００以下であり、さらに好ましくは１００以上３，０００以下であり、よりさらに好ましくは１５０以上２，９００以下であり、特に好ましくは２５０以上１，５００以下である。 The weight average molecular weight of the polymerizable compound (C) is preferably 50 or more and 4,000 or less, more preferably 70 or more and 3,500 or less, even more preferably 100 or more and 3,000 or less, even more preferably 150 or more and 2,900 or less, and particularly preferably 250 or more and 1,500 or less.
　重合性化合物（Ｃ）の含有率は、着色硬化性樹脂組成物の固形分の総量に対して、例えば１質量％以上９９質量％以下であってよく、好ましくは３質量％以上９０質量％以下であり、より好ましくは５質量％以上８０質量％以下であり、さらに好ましくは７質量％以上７０質量％以下である。 The content of the polymerizable compound (C) may be, for example, 1% by mass or more and 99% by mass or less, preferably 3% by mass or more and 90% by mass or less, more preferably 5% by mass or more and 80% by mass or less, and even more preferably 7% by mass or more and 70% by mass or less, based on the total amount of solids in the colored curable resin composition.
＜重合開始剤（Ｄ）＞
　重合開始剤（Ｄ）は、光や熱の作用により活性ラジカル、酸等を発生し、重合を開始しうる化合物であればよい。 <Polymerization initiator (D)>
The polymerization initiator (D) may be any compound that can generate active radicals, acids, etc. by the action of light or heat and initiate polymerization.
　重合開始剤（Ｄ）として、Ｏ－アシルオキシム化合物、アルキルフェノン化合物、ビイミダゾール化合物、トリアジン化合物及びアシルホスフィンオキサイド化合物等が挙げられる。 Examples of the polymerization initiator (D) include O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.
　前記Ｏ－アシルオキシム化合物は、式（ｄ－１）で表される部分構造を有する化合物である。式中、＊は結合手を表す。 The O-acyloxime compound is a compound having a partial structure represented by formula (d-1). In the formula, * represents a bond.
Figure JPOXMLDOC01-appb-I000030
Figure JPOXMLDOC01-appb-I000030
　前記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－フェニルスルファニルフェニル）－３－シクロヘキシルプロパン－１－オン－２－イミン等が挙げられる。イルガキュアＯＸＥ０１（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）、イルガキュアＯＸＥ０２（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）（以上、ＢＡＳＦ製）、Ｎ－１９１９（ＡＤＥＫＡ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、Ｎ－アセチルオキシ－１－（４－フェニルスルファニルフェニル）－３－シクロヘキシルプロパン－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）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－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－イミン及び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１種が好ましく、Ｎ－アセチルオキシ－１－（４－フェニルスルファニルフェニル）－３－シクロヘキシルプロパン－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－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－イミンがより好ましい。これらのＯ－アシルオキシム化合物であると、高明度な光学フィルタが得られる傾向にある。 Examples of the O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-di N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, and the like. Commercially available products such as IRGACURE OXE01 (N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine), IRGACURE OXE02 (N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine) (both manufactured by BASF), and N-1919 (manufactured by ADEKA) may also be used. Among them, the O-acyloxime compounds include N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine and N-benzoyloxy- At least one selected from the group consisting of 1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine is preferred, with N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, and N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine being more preferred. These O-acyloxime compounds tend to produce optical filters with high brightness.
　前記アルキルフェノン化合物は、式（ｄ－２）で表される部分構造又は式（ｄ－３）で表される部分構造を有する化合物である。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。式中、＊は結合手を表す。 The alkylphenone compound is a compound having a partial structure represented by formula (d-2) or a partial structure represented by formula (d-3). In these partial structures, the benzene ring may have a substituent. In the formula, * represents a bond.
Figure JPOXMLDOC01-appb-I000031
Figure JPOXMLDOC01-appb-I000031
　式（ｄ－２）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３６９、９０７、３７９（以上、ＢＡＳＦ製）等の市販品を用いてもよい。 Examples of compounds having the partial structure represented by formula (d-2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one. Commercially available products such as Irgacure 369, 907, and 379 (all manufactured by BASF) may also be used.
　式（ｄ－３）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（ｄ－２）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 formula (d-3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyl dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (d-2).
　前記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 compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-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, and 2,4-bis(trichloromethyl)-6- Examples include [2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.
　前記アシルホスフィンオキサイド化合物としては、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製）等の市販品を用いてもよい。 The acylphosphine oxide compound may be 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may also be used.
　前記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号公報等参照）、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号公報等参照）、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号公報等参照）等が挙げられる。中でも、下記式で表される化合物及びこれらの混合物が好ましい。 The biimidazole compound may, for example, be 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxy phenyl) 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, JP-B-48-38403 and JP-A-62-174204), and biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboalkoxy groups (see, for example, JP-A-7-10913). Among these, the compounds represented by the following formula and mixtures thereof are preferred.
Figure JPOXMLDOC01-appb-I000032
Figure JPOXMLDOC01-appb-I000032
　さらに重合開始剤（Ｄ）としては、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（Ｄ１）（特にアミン類）と組み合わせて用いることが好ましい。 Further examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with the polymerization initiator aid (D1) (especially amines) described below.
　酸を発生する重合開始剤としては、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や、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 polymerization initiators that generate acid include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium hexafluoroantimonate, as well as nitrobenzyl tosylates and benzoin tosylates.
　重合開始剤（Ｄ）としては、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、Ｏ－アシルオキシム化合物及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１種を含む重合開始剤が好ましく、Ｏ－アシルオキシム化合物及び又はビイミダゾール化合物を含む重合開始剤がより好ましく、Ｏ－アシルオキシム化合物を含む重合開始剤がさらに好ましい。 As the polymerization initiator (D), a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a biimidazole compound is preferred, a polymerization initiator containing an O-acyloxime compound and/or a biimidazole compound is more preferred, and a polymerization initiator containing an O-acyloxime compound is even more preferred.
　重合開始剤（Ｄ）の含有量は、樹脂（Ｂ）及び重合性化合物（Ｃ）の合計量１００質量部に対して、好ましくは０．１質量部以上３０質量部以下であり、より好ましくは１質量部以上２０質量部以下である。重合開始剤（Ｄ）の含有量が、前記の範囲内にあると、高感度化して露光時間が短縮される傾向があるため光学フィルタの生産性が向上する。 The content of the polymerization initiator (D) is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, thereby improving the productivity of the optical filter.
＜重合開始助剤（Ｄ１）＞
　重合開始助剤（Ｄ１）は、重合開始剤（Ｄ）によって重合が開始された重合性化合物（Ｃ）の重合を促進するために用いられる化合物、もしくは増感剤である。重合開始助剤（Ｄ１）を含む場合、通常、重合開始剤（Ｄ）と組み合わせて用いられる。 <Polymerization Initiator Auxiliary Agent (D1)>
The polymerization initiation aid (D1) is a compound used to promote the polymerization of the polymerizable compound (C) whose polymerization has been initiated by the polymerization initiator (D), or a sensitizer. When the polymerization initiation aid (D1) is contained, it is usually used in combination with the polymerization initiator (D).
　重合開始助剤（Ｄ１）としては、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及びカルボン酸化合物等が挙げられる。 Examples of the polymerization initiator aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.
　アミン化合物としては、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）ベンゾフェノン及び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、好ましくは４，４’－ビス（ジエチルアミノ）ベンゾフェノンが挙げられる。また、アミン化合物として、ＥＡＢ－Ｆ（保土谷化学工業（株）製）等の市販品を用いてもよい。 Amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone, with 4,4'-bis(diethylamino)benzophenone being preferred. Commercially available amine compounds such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may also be used.
　アルコキシアントラセン化合物としては、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及び２－エチル－９，１０－ジブトキシアントラセン等が挙げられる。 Alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and 2-ethyl-9,10-dibutoxyanthracene.
　チオキサントン化合物としては、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及び１－クロロ－４－プロポキシチオキサントン等が挙げられる。 Thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.
　カルボン酸化合物としては、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－ナフチルグリシン及びナフトキシ酢酸等が挙げられる。 Carboxylic acid compounds include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.
　これらの重合開始助剤（Ｄ１）を用いる場合、その含有量は、着色硬化性樹脂組成物に含まれる全樹脂（Ｂ）及び重合性化合物（Ｃ）の合計量１００質量部に対して、好ましくは０．１質量部以上３０質量部以下、より好ましくは１質量部以上２０質量部以下である。 When these polymerization initiator aids (D1) are used, the content is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the total amount of all resins (B) and polymerizable compounds (C) contained in the colored curable resin composition.
＜溶剤（Ｅ）＞
　溶剤（Ｅ）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（Ｅ）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－及び－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。これらの溶剤は、２種以上を併用してもよい。 <Solvent (E)>
The solvent (E) is not particularly limited, and any solvent commonly used in the relevant field can be used.
Examples of the solvent (E) include ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc. Two or more of these solvents may be used in combination.
　エステル溶剤としては、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及びγ－ブチロラクトン等が挙げられる。 Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and gamma-butyrolactone.
　エーテル溶剤としては、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、フェネトール及びメチルアニソール等が挙げられる。 Ether solvents 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, propylene glycol monoethyl 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 methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and methylanisole.
　エーテルエステル溶剤としては、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及びジプロピレングリコールメチルエーテルアセテート等が挙げられる。 Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate, Examples of such ether acetates include ethyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol methyl ether acetate.
　ケトン溶剤としては、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、シクロペンタノン、シクロヘキサノン及びイソホロン等が挙げられる。 Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.
　アルコール溶剤としては、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及びグリセリン等が挙げられる。 Alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.
　芳香族炭化水素溶剤としては、ベンゼン、トルエン、キシレン、メシチレン等が挙げられる。 Aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene, etc.
　アミド溶剤としては、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド及びＮ－メチルピロリドン等が挙げられる。 Amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.
　溶剤（Ｅ）としては、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、乳酸エチル及びシクロヘキサノンが好ましく、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がより好ましい。 As the solvent (E), propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and cyclohexanone are preferred, and propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether are more preferred.
　溶剤（Ｅ）を含む場合、溶剤（Ｅ）の含有率は、着色硬化性樹脂組成物の総量に対して、通常９９．９９質量％以下であり、好ましくは４０質量％以上９９質量％以下であり、より好ましくは５０質量％以上９７質量％以下であり、さらに好ましくは７０質量％以上９６質量％以下であり、よりさらに好ましくは７３質量％以上９５質量％以下である。言い換えると、着色硬化性樹脂組成物の固形分の総量は、通常０．０１質量％以上であり、好ましくは１質量％以上６０質量％以下であり、より好ましくは３質量％以上５０質量％以下であり、さらに好ましくは４質量％以上３０質量％以下であり、よりさらに好ましくは５質量％以上２７質量％以下である。溶剤（Ｅ）の含有率が前記の範囲内にあると、塗布時の平坦性が良好になり、また光学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 (E) is included, the content of the solvent (E) is usually 99.99% by mass or less, preferably 40% by mass or more and 99% by mass or less, more preferably 50% by mass or more and 97% by mass or less, even more preferably 70% by mass or more and 96% by mass or less, and even more preferably 73% by mass or more and 95% by mass or less, based on the total amount of the colored curable resin composition. In other words, the total amount of solids in the colored curable resin composition is usually 0.01% by mass or more, preferably 1% by mass or more and 60% by mass or less, more preferably 3% by mass or more and 50% by mass or less, even more preferably 4% by mass or more and 30% by mass or less, and even more preferably 5% by mass or more and 27% by mass or less. When the content of the solvent (E) is within the above range, the flatness during application is good, and the color density is not insufficient when an optical filter is formed, so that the display characteristics tend to be good.
＜チオール化合物（Ｔ）＞
　本発明の着色硬化性樹脂組成物は、チオール化合物（Ｔ）を含んでいてもよい。
チオール化合物（Ｔ）は、分子内にスルファニル基（－ＳＨ）を有する化合物である。 <Thiol Compound (T)>
The colored curable resin composition of the present invention may contain a thiol compound (T).
The thiol compound (T) is a compound having a sulfanyl group (-SH) in the molecule.
　分子内にスルファニル基を１つ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 compounds having one sulfanyl group in the molecule include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanylbenzoxazole, 2-sulfanylnicotinic acid, 2-sulfanylpyridine, 2-sulfanylpyridin-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-propylpyrimidine, 2-sulfanyl-4-methylpyrimidine, 2-sulfanylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-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-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-disulfanyl-1,3,4-thiadiazole, (furan-2-yl)methanethiol, 2-sulfanyl-5-thiazolidone, 2-sulfanylthiazoline, 2-sulfanyl-4(3H)-quinazolinone, 1-phenyl-1H-tetrazole-5-thiol , 2-quinolinethiol, 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-purinethiol, 6-sulfanylpurine, 4-sulfanyl-1H-pyrazolo[2,4-d]pyrimidine, etc.
　分子内にスルファニル基を２つ以上有する化合物としては、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）、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 with two or more sulfanyl groups in the molecule include hexanedithiol, decanedithiol, 1,4-bis(methylsulfanyl)benzene, butanediol bis(3-sulfanylpropionate), butanediol bis(3-sulfanyl acetate), ethylene glycol bis(3-sulfanyl acetate), trimethylolpropane tris(3-sulfanyl acetate), butanediol bis(3-sulfanylpropionate), trimethylolpropane tris(3-sulfanyl acetate), Examples include propane tris(3-sulfanylpropionate), trimethylolpropane tris(3-sulfanyl acetate), pentaerythritol tetrakis(3-sulfanylpropionate), pentaerythritol tetrakis(3-sulfanyl acetate), trishydroxyethyl tris(3-sulfanylpropionate), pentaerythritol tetrakis(3-sulfanyl butyrate), and 1,4-bis(3-sulfanylbutyloxy)butane.
　チオール化合物（Ｔ）の含有量は、重合開始剤（Ｄ）１００質量部に対して、好ましくは０．５～５０質量部、より好ましくは５～４５質量部であり、更に好ましくは１０～４０質量部である。チオール化合物（Ｔ）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。 The content of the thiol compound (T) is preferably 0.5 to 50 parts by mass, more preferably 5 to 45 parts by mass, and even more preferably 10 to 40 parts by mass, per 100 parts by mass of the polymerization initiator (D). When the content of the thiol compound (T) is within this range, the sensitivity tends to be high and the developability tends to be good.
＜レベリング剤（Ｆ）＞
　レベリング剤（Ｆ）としては、シリコーン系界面活性剤、フッ素系界面活性剤及びフッ素原子を有するシリコーン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 (F)>
Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms, which may have a polymerizable group in the side chain.
　シリコーン系界面活性剤としては、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。具体的には、トーレシリコーンＤＣ３ＰＡ、同ＳＨ７ＰＡ、同ＤＣ１１ＰＡ、同ＳＨ２１ＰＡ、同ＳＨ２８ＰＡ、同ＳＨ２９ＰＡ、同ＳＨ３０ＰＡ、同ＳＨ８４００（商品名：東レ・ダウコーニング（株）製）、ＫＰ３２１、ＫＰ３２２、ＫＰ３２３、ＫＰ３２４、ＫＰ３２６、ＫＰ３４０、ＫＰ３４１（信越化学工業（株）製）、ＴＳＦ４００、ＴＳＦ４０１、ＴＳＦ４１０、ＴＳＦ４３００、ＴＳＦ４４４０、ＴＳＦ４４４５、ＴＳＦ４４４６、ＴＳＦ４４５２及び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 silicone surfactants include surfactants having a siloxane bond in the molecule. Specific examples include Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (product names: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan, LLC).
　フッ素系界面活性剤としては、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。具体的には、フロラード（登録商標）ＦＣ４３０、同ＦＣ４３１（住友スリーエム（株）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（株）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（株）製）、サーフロン（登録商標）Ｓ３８１、同Ｓ３８２、同ＳＣ１０１、同ＳＣ１０５（ＡＧＣ（株）製）及び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。 Fluorosurfactants include surfactants having a fluorocarbon chain in the molecule. Specific examples include Fluorad (registered trademark) FC430 and FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, and RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, EF303, EF351, and EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, and SC105 (manufactured by AGC Corporation), and E5844 (manufactured by Daikin Fine Chemicals Research Institute Ltd.).
　フッ素原子を有するシリコーン系界面活性剤としては、分子内にシロキサン結合及び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。具体的には、メガファック（登録商標）Ｒ０８、同ＢＬ２０、同Ｆ４７５、同Ｆ４７７及び同Ｆ４４３（ＤＩＣ（株）製）等が挙げられる。 Examples of silicone surfactants containing fluorine atoms include surfactants that have siloxane bonds and fluorocarbon chains in the molecule. Specific examples include Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).
　レベリング剤（Ｆ）を含有する場合、レベリング剤（Ｆ）の含有率は、着色硬化性樹脂組成物の総量に対して、好ましくは０．０００５質量％以上１質量％以下であり、より好ましくは０．００１質量％以上０．５質量％以下であり、さらに好ましくは０．００５質量％以上０．１質量％以下である。なおこの含有量に、顔料分散剤の含有量は含まれない。レベリング剤（Ｆ）の含有率が前記の範囲内にあると、光学フィルタの平坦性を良好にすることができる。 When the leveling agent (F) is contained, the content of the leveling agent (F) is preferably 0.0005% by mass or more and 1% by mass or less, more preferably 0.001% by mass or more and 0.5% by mass or less, and even more preferably 0.005% by mass or more and 0.1% by mass or less, based on the total amount of the colored curable resin composition. Note that this content does not include the content of the pigment dispersant. When the content of the leveling agent (F) is within the above range, the flatness of the optical filter can be improved.
＜その他の成分＞
　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、クエンチャー、酸化防止剤、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もよい。
　密着促進剤としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２－メトキシエトキシ）シラン、３－グリシジルオキシプロピルトリメトキシシラン、３－グリシジルオキシプロピルメチルジメトキシシラン、３－グリシジルオキシプロピルメチルジエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－クロロプロピルメチルジメトキシシラン、３－クロロプロピルトリメトキシシラン、３－メタクリロイルオキシプロピルトリメトキシシラン、３－スルファニルプロピルトリメトキシシラン、３－イソシアナトプロピルトリエトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジエトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン及びＮ－フェニル－３－アミノプロピルトリエトキシシラン等が挙げられる。 <Other ingredients>
The colored curable resin composition may contain additives known in the technical field, such as a filler, another polymer compound, an adhesion promoter, a quencher, an antioxidant, a light stabilizer, and a chain transfer agent, as necessary.
Examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-sulfur Examples of the silane include anylpropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane.
＜着色硬化性樹脂組成物の製造方法＞
　着色硬化性樹脂組成物は、着色剤（Ａ）、金属化合物（Ｇ）、樹脂（Ｂ）、重合性化合物（Ｃ）、重合開始剤（Ｄ）、並びに必要に応じて用いられる重合開始助剤（Ｄ１）、溶剤（Ｅ）、レベリング剤（Ｆ）及びその他の成分を混合することにより調製できる。混合は公知又は慣用の装置や条件により行うことができる。
　着色剤（Ａ）は、予め溶剤（Ｅ）の一部又は全部と混合し、平均粒子径が０．２μｍ以下程度となるまで、ビーズミル等を用いて分散させて得られた着色剤含有液として用いてもよく、着色剤含有液として用いることが好ましい。この際、必要に応じて前記分散剤、樹脂（Ｂ）の一部又は全部を配合してもよい。このようにして得られた着色剤含有液に、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。
　また着色剤（Ａ）として染料を含む場合の該染料は、予め溶剤（Ｅ）の一部又は全部に溶解させて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。 <Method for producing colored curable resin composition>
The colored curable resin composition can be prepared by mixing the colorant (A), the metal compound (G), the resin (B), the polymerizable compound (C), the polymerization initiator (D), and optionally the polymerization initiator aid (D1), the solvent (E), the leveling agent (F), and other components. The mixing can be carried out using known or conventional equipment and conditions.
The colorant (A) may be used as a colorant-containing liquid obtained by mixing with a part or all of the solvent (E) in advance and dispersing using a bead mill or the like until the average particle size becomes about 0.2 μm or less, and it is preferable to use it as a colorant-containing liquid. In this case, the dispersant and a part or all of the resin (B) may be blended as necessary. The remaining components are mixed into the colorant-containing liquid obtained in this way to a predetermined concentration, whereby the desired colored curable resin composition can be prepared.
In addition, when a dye is contained as the colorant (A), the dye may be dissolved in advance in a part or all of the solvent (E) to prepare a solution. The solution is preferably filtered through a filter having a pore size of about 0.01 to 1 μm.
＜光学フィルタ（カラーフィルタ）の製造方法＞
　本発明の着色硬化性樹脂組成物から光学フィルタ（カラーフィルタ）を形成することができる。着色パターンを製造する方法としては、フォトリソグラフ法、インクジェット法、印刷法等が挙げられる。中でも、フォトリソグラフ法が好ましい。フォトリソグラフ法は、前記着色硬化性樹脂組成物を基板に塗布し、乾燥させて着色組成物層を形成し、フォトマスクを介して該着色組成物層を露光して、現像する方法である。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、及び／又は現像しないことにより、前記着色組成物層の硬化物である着色塗膜を形成することができる。このように形成した着色パターンや着色塗膜が本発明の光学フィルタ（カラーフィルタ）である。 <Method of manufacturing optical filters (color filters)>
An optical filter (color filter) can be formed from the colored curable resin composition of the present invention. Examples of methods for producing a colored pattern include a photolithography method, an inkjet method, and a printing method. Among them, the photolithography method is preferred. The photolithography method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithography method, a colored coating film, which is a cured product of the colored composition layer, can be formed by not using a photomask during exposure and/or not developing. The colored pattern or colored coating film thus formed is the optical filter (color filter) of the present invention.
　作製する光学フィルタ（カラーフィルタ）の膜厚は、特に限定されず、目的や用途等に応じて適宜調整することができ、例えば、３０μｍ以下、好ましくは２０μｍ以下、より好ましくは６μｍ以下、さらに好ましくは４．５μｍ以下であり、好ましくは０．１μｍ以上、より好ましくは０．２μｍ以上、さらに好ましくは０．３μｍ以上である。 The film thickness of the optical filter (color filter) to be produced is not particularly limited and can be adjusted appropriately depending on the purpose and application, and is, for example, 30 μm or less, preferably 20 μm or less, more preferably 6 μm or less, even more preferably 4.5 μm or less, and is preferably 0.1 μm or more, more preferably 0.2 μm or more, even more preferably 0.3 μm or more.
　基板としては、石英ガラス、ホウケイ酸ガラス、アルミナケイ酸塩ガラス、表面をシリカコートしたソーダライムガラスなどのガラス板や、ポリカーボネート、ポリメタクリル酸メチル、ポリエチレンテレフタレートなどの樹脂板、シリコン、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を形成したものが用いられる。これらの基板上には、別の光学フィルタ層（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。またシリコン基板上にＨＭＤＳ（ヘキサメチルジシラザン）処理を施した基板を使用してもよい。 The substrate may be a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, or soda lime glass with a silica-coated surface; a resin plate such as polycarbonate, polymethylmethacrylate, or polyethylene terephthalate; silicon; or a substrate on which an aluminum, silver, or silver/copper/palladium alloy thin film is formed. On these substrates, another optical filter layer (color filter layer), a resin layer, a transistor, a circuit, or the like may be formed. A silicon substrate treated with HMDS (hexamethyldisilazane) may also be used.
　フォトリソグラフ法による各色画素の形成は、公知又は慣用の装置や条件で行うことができる。例えば、下記のようにして作製することができる。
　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）及び／又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乾燥させ、平滑な着色組成物層を得る。塗布方法としては、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。加熱乾燥を行う場合の温度は、３０℃以上１２０℃以下が好ましく、５０℃以上１１０℃以下がより好ましい。また加熱時間としては、１０秒間以上６０分間以下であることが好ましく、３０秒間以上３０分間以下であることがより好ましい。
　減圧乾燥を行う場合は、５０Ｐａ以上１５０Ｐａ以下の圧力下、２０℃以上２５℃以下の温度範囲で行うことが好ましい。着色組成物層の膜厚は、特に限定されず、目的とする光学フィルタの膜厚に応じて適宜選択すればよい。 The formation of each color pixel by photolithography can be carried out using known or conventional equipment and conditions. For example, the pixel can be produced as follows.
First, the colored curable resin composition is applied onto a substrate, and then dried by heating and drying (pre-baking) and/or drying under reduced pressure to remove volatile components such as a solvent, thereby obtaining a smooth colored composition layer. Examples of the application method include spin coating, slit coating, and slit and spin coating. The temperature at which the heat drying is performed is preferably 30° C. or higher and 120° C. or lower, and more preferably 50° C. or higher and 110° C. or lower. The heating time is preferably 10 seconds or higher and 60 minutes or lower, and more preferably 30 seconds or higher and 30 minutes or lower.
When drying under reduced pressure is performed, it is preferable to perform the drying under a pressure of 50 Pa or more and 150 Pa or less at a temperature range of 20° C. or more and 25° C. or less. The thickness of the coloring composition layer is not particularly limited and may be appropriately selected depending on the thickness of the intended optical filter.
　次に、着色組成物層は、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露光される。該フォトマスク上のパターンは特に限定されず、目的とする用途に応じたパターンが用いられる。また、露光面全体に均一に平行光線を照射することや、フォトマスクと着色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、マスクアライナ及びステッパ等の露光装置を使用することが好ましい。着色塗膜を形成する場合には、フォトマスクを用いずに露光すればよい。 The colored composition layer is then exposed through a photomask to form the desired colored pattern. There are no particular limitations on the pattern on the photomask, and a pattern appropriate for the intended use is used. In addition, it is preferable to use an exposure device such as a mask aligner or stepper, since it is possible to uniformly irradiate the entire exposed surface with parallel light and to accurately align the photomask with the substrate on which the colored composition layer is formed. When a colored coating film is formed, exposure can be performed without using a photomask.
　露光に用いられる光源としては、２５０ｎｍ以上４５０ｎｍ以下の波長の光を発生する光源が好ましい。例えば、３５０ｎｍ未満の光を、この波長域をカットするフィルタを用いてカットしたり、４３６ｎｍ付近、４０８ｎｍ付近、３６５ｎｍ付近の光を、これらの波長域を取り出すバンドパスフィルタを用いて選択的に取り出したりしてもよい。具体的には、水銀灯、発光ダイオード、メタルハライドランプ、ハロゲンランプ等が挙げられる。 The light source used for exposure is preferably a light source that generates light with a wavelength of 250 nm or more and 450 nm or less. For example, light less than 350 nm may be cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, and 365 nm may be selectively extracted using a bandpass filter that extracts these wavelength ranges. Specific examples include mercury lamps, light-emitting diodes, metal halide lamps, and halogen lamps.
　露光後の着色組成物層を現像液に接触させて現像することにより、基板上に着色塗膜（着色パターン）が形成される。現像により、着色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、例えば、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。これらのアルカリ性化合物の水溶液中の濃度は、好ましくは０．０１質量％以上１０質量％以下であり、より好ましくは０．０３質量％以上５質量％以下である。さらに、現像液は、界面活性剤を含んでいてもよい。現像方法は、パドル法、ディッピング法及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。
　現像後の基板は、水洗されることが好ましい。 The colored composition layer after exposure is brought into contact with a developer and developed to form a colored coating film (colored pattern) on the substrate. The unexposed portion of the colored composition layer is dissolved in the developer and removed by development. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.03% by mass or more and 5% by mass or less. Furthermore, the developer may contain a surfactant. The development method may be any of a paddle method, a dipping method, and a spray method. Furthermore, the substrate may be tilted at any angle during development.
After development, the substrate is preferably washed with water.
　さらに、得られた着色パターン又は着色塗膜に、ポストベークを行うことが好ましい。ポストベーク温度は、８０℃以上２５０℃以下が好ましく、１００℃以上２４５℃以下がより好ましい。ポストベーク時間は、１分間以上１２０分間以下が好ましく、２分間以上３０分間以下がより好ましい。
　このようにして得られた着色パターン及び着色塗膜は、カラーフィルタとして有用である。 Furthermore, it is preferable to perform post-baking on the obtained colored pattern or colored coating film. The post-baking temperature is preferably from 80° C. to 250° C., and more preferably from 100° C. to 245° C. The post-baking time is preferably from 1 minute to 120 minutes, and more preferably from 2 minutes to 30 minutes.
The colored pattern and colored coating film thus obtained are useful as a color filter.
＜表示装置、固体撮像素子＞
　前記光学フィルタ（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）、及び固体撮像素子等に用いられる光学フィルタ（カラーフィルタ）として有用である。 <Display device, solid-state image sensor>
The optical filter (color filter) is useful as an optical filter (color filter) for use in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.), solid-state imaging devices, and the like.
　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、前・後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勿論可能であり、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「質量部」を、「％」は「質量％」を意味する。 The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to the following examples, and it is of course possible to carry out the invention with appropriate modifications within the scope of the intent described above and below, all of which are included in the technical scope of the present invention. In the following, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".
　以下の実施例において、化合物の構造は質量分析（ＬＣ；Ａｇｉｌｅｎｔ製１２００型、ＭＡＳＳ；Ａｇｉｌｅｎｔ製ＬＣ／ＭＳＤ６１３０型）、1Ｈ－ＮＭＲ（Ｖａｒｉａｎ製４００－ＭＲ）で確認した。 In the following examples, the structures of the compounds were confirmed by mass spectrometry (LC; Agilent Model 1200, MASS; Agilent Model LC/MSD6130) and 1 H-NMR (Varian Model 400-MR).
　樹脂のポリスチレン換算の重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）の測定は、ＧＰＣ法により以下の条件で行った。
　装置：ＨＬＣ－８１２０ＧＰＣ（東ソー（株）製）
　カラム：ＴＳＫ－ＧＥＬＧ２０００ＨＸＬ
　カラム温度：４０℃
　溶媒：テトラヒドロフラン
　流速：１．０ｍＬ／分
　分析試料の固形分濃度：０．００１～０．０１質量％
　注入量：５０μＬ
　検出器：ＲＩ
　校正用標準物質：ＴＳＫ　ＳＴＡＮＤＡＲＤ　ＰＯＬＹＳＴＹＲＥＮＥ　Ｆ－４０、Ｆ－４、Ｆ－２８８、Ａ－２５００、Ａ－５００（東ソー（株）製）
　上記で得られたポリスチレン換算の重量平均分子量及び数平均分子量の比（Ｍｗ／Ｍｎ）を分散度とした。 The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by GPC under the following conditions.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG2000HXL
Column temperature: 40°C
Solvent: tetrahydrofuran Flow rate: 1.0 mL/min Solids concentration of analytical sample: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector: RI
Calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio of the weight average molecular weight and the number average molecular weight (Mw/Mn) calculated in terms of polystyrene obtained above was taken as the dispersity.
＜合成例１＞
　式（ＩＩ－Ｘ）で表される化合物４０．５部と２，６－キシリジン（東京化成工業（株）製）６０．５部とを遮光条件下混合し、Ｎ－メチルピリドン２００部中、１５０℃で８時間攪拌した。得られた反応液を室温まで冷却後、水１２００部、３５％塩酸７５部の混合液中に添加し室温で１時間攪拌したところ、結晶が析出した。析出した結晶を吸引濾過の残渣として取得しメタノール１００部にて洗浄後、１２時間６０℃減圧乾燥し、式（ＩＩ－１）で表される化合物４９部を得た。収率は８５％であった。 <Synthesis Example 1>
40.5 parts of the compound represented by formula (II-X) and 60.5 parts of 2,6-xylidine (Tokyo Chemical Industry Co., Ltd.) were mixed under light-shielding conditions, and the mixture was stirred in 200 parts of N-methylpyridone at 150° C. for 8 hours. The resulting reaction solution was cooled to room temperature, and then added to a mixed solution of 1200 parts of water and 75 parts of 35% hydrochloric acid and stirred at room temperature for 1 hour, whereby crystals were precipitated. The precipitated crystals were collected as a residue by suction filtration, washed with 100 parts of methanol, and then dried under reduced pressure at 60° C. for 12 hours, to obtain 49 parts of the compound represented by formula (II-1). The yield was 85%.
Figure JPOXMLDOC01-appb-I000033
Figure JPOXMLDOC01-appb-I000033
　式（ＩＩ－１）で表される化合物の同定
（質量分析）イオン化モード＝ＥＳＩ＋：　ｍ／ｚ＝[Ｍ＋Ｈ]+ ５７５
　　　　　　　　　　　　　　Ｅｘａｃｔ　Ｍａｓｓ：　５７４ Identification of the compound represented by formula (II-1) (mass spectrometry) Ionization mode = ESI+: m/z = [M+H] + 575
Exact Mass: 574
＜合成例２＞
　還流冷却器、滴下ロート及び攪拌機を備えたフラスコ内に窒素を適量流し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３４０部を入れ、攪拌しながら８０℃まで加熱した。次いで、アクリル酸５７部、３，４－エポキシトリシクロ［５．２．１．０2,6］デカン－８－イルアクリレート及び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）５４部、ベンジルメタクリレート２３９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７３部の混合溶液を５時間かけて滴下した。一方、重合開始剤２，２－アゾビス（２，４－ジメチルバレロニトリル）４０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１９７部に溶解した溶液を６時間かけて滴下した。開始剤溶液の滴下終了後、８０℃で３時間保持した後、室温まで冷却して、Ｂ型粘度計（２３℃）で測定した粘度１２７ｍＰａｓ、固形分３７．０重量％の共重合体（樹脂（Ｂ－１））溶液を得た。生成した共重合体の重量平均分子量Ｍｗは９．４×１０3、分散度は１．８９、固形分換算の酸価は１１４ｍｇ－ＫＯＨ／ｇであった。樹脂（Ｂ－１）は、以下の構造単位を有する。 <Synthesis Example 2>
A suitable amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the atmosphere with nitrogen, 340 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80°C while stirring. Next, a mixed solution of 57 parts of acrylic acid, 54 parts of a mixture of 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-9-yl acrylate (content ratio is 1:1 by molar ratio), 239 parts of benzyl methacrylate, and 73 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. Meanwhile, a solution of 40 parts of polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 197 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition of the initiator solution, the mixture was kept at 80°C for 3 hours and then cooled to room temperature to obtain a copolymer (resin (B-1)) solution having a solid content of 37.0% by weight and a viscosity of 127 mPas measured with a Brookfield viscometer (23°C). The weight average molecular weight Mw of the produced copolymer was 9.4 x 10 3 , the dispersity was 1.89, and the acid value calculated as solid content was 114 mg-KOH/g. Resin (B-1) has the following structural units.
Figure JPOXMLDOC01-appb-I000034
Figure JPOXMLDOC01-appb-I000034
＜合成例３＞
　撹拌装置、滴下ロート、コンデンサー、温度計、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アセテート２７６．８部を取り、窒素置換しながら撹拌し１２０℃に昇温した。次いで、２－エチルヘキシルアクリレート９２．４部、グリシジルメタクリレート１８４．９部及びジシクロペンタニルメタクリレート１２．３部からなるモノマー混合物に、３５．３部のｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエート（重合開始剤）を添加したものを滴下ロートから２時間にわたって前記フラスコ中に滴下した。滴下終了後、１２０℃でさらに３０分間撹拌して共重合反応を行い、付加共重合体を生成させた。その後、フラスコ内を空気に置換し、アクリル酸９３．７部、トリフェニルホスフィン（触媒）１．５部およびメトキノン（重合禁止剤）０．８部を上記の付加共重合体溶液中に投入し、１１０℃で１０時間にわたり反応を続け、グリシジルメタクリレート由来のエポキシ基とアクリル酸の反応によりエポキシ基を開裂すると同時にポリマーの側鎖に重合性不飽和結合を導入した。次いで、反応系に無水コハク酸２４．２部を加え、１１０℃で１時間にわたり反応を続け、エポキシ基の開裂により生じたヒドロキシ基と無水コハク酸を反応させて側鎖にカルボキシル基を導入し、ポリマーを得た。最後に反応溶液に、プロピレングリコールモノメチルエーテルアセテート３８３．３部を加え、ポリマー固形分４０％のポリマー（樹脂（Ｂ－２））溶液を得た。生成した共重合体（ポリマー；樹脂（Ｂ－２））の重量平均分子量Ｍｗは６．３×１０3、固形分換算の酸価は３４ｍｇ－ＫＯＨ／ｇであった。 <Synthesis Example 3>
276.8 parts of propylene glycol monomethyl ether acetate was taken in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the mixture was stirred while replacing with nitrogen and heated to 120°C. Next, a monomer mixture consisting of 92.4 parts of 2-ethylhexyl acrylate, 184.9 parts of glycidyl methacrylate, and 12.3 parts of dicyclopentanyl methacrylate, to which 35.3 parts of tert-butylperoxy-2-ethylhexanoate (polymerization initiator) had been added, was dropped into the flask from the dropping funnel over 2 hours. After the dropwise addition was completed, the mixture was stirred for another 30 minutes at 120°C to carry out a copolymerization reaction, and an addition copolymer was produced. Thereafter, the flask was replaced with air, and 93.7 parts of acrylic acid, 1.5 parts of triphenylphosphine (catalyst) and 0.8 parts of methoquinone (polymerization inhibitor) were added to the addition copolymer solution, and the reaction was continued at 110°C for 10 hours, and the epoxy group derived from glycidyl methacrylate was reacted with acrylic acid to cleave the epoxy group, and at the same time, a polymerizable unsaturated bond was introduced into the side chain of the polymer. Next, 24.2 parts of succinic anhydride were added to the reaction system, and the reaction was continued at 110°C for 1 hour, and the hydroxyl group generated by the cleavage of the epoxy group was reacted with succinic anhydride to introduce a carboxyl group into the side chain, thereby obtaining a polymer. Finally, 383.3 parts of propylene glycol monomethyl ether acetate was added to the reaction solution, and a polymer (resin (B-2)) solution with a polymer solid content of 40% was obtained. The weight average molecular weight Mw of the produced copolymer (polymer; resin (B-2)) was 6.3×10 3 , and the acid value calculated as solid content was 34 mg-KOH/g.
Figure JPOXMLDOC01-appb-I000035
Figure JPOXMLDOC01-appb-I000035
＜実施例１＞
（１）着色分散液１の作製
　化合物（ＩＩ－１）８０．０部、分散剤（ＢＹＫ社製　ＢＹＫＬＰＮ－６９１９）（固形分換算）２９．１部、樹脂Ｂ－１（固形分換算）２９．１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８６１．８部、及び０．２ｍｍのジルコニアビーズ１５００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着色分散液１を得た。 Example 1
(1) Preparation of Colored Dispersion 1 80.0 parts of compound (II-1), 29.1 parts of dispersant (BYKLPN-6919 manufactured by BYK Corporation) (solid content equivalent), 29.1 parts of resin B-1 (solid content equivalent), 861.8 parts of propylene glycol monomethyl ether acetate, and 1500 parts of 0.2 mm zirconia beads were mixed, and the resulting mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU Corporation). Thereafter, the zirconia beads were removed by filtration to obtain a colored dispersion 1.
（２）着色硬化性樹脂組成物１の作製
　下記の成分を混合することにより、着色硬化性樹脂組成物１を得た。
着色剤（Ａ）：着色分散液１　　　　　　　　　　　　　　　４０７．１部
金属化合物（Ｇ）：ビス（８－キノリノラト)銅(ＩＩ)　　　　　　５．３部
樹脂（Ｂ）：合成例３で得られた樹脂（Ｂ－２）　　　　　　　５１．８部（固形換算）重合性化合物（Ｃ）：（ジペンタエリスリトールポリアクリレート：商品名Ａ－９５５０、新中村化学工業（株）製）　　　　　　　　　　　　　　　４２．５部（固形換算）
重合開始剤（Ｄ）：Ｎ－アセチルオキシ－１－（４－フェニルスルファニルフェニル）－３－シクロヘキシルプロパン－１－オン－２－イミン：商品名ＴＲ－ＰＢＧ３２７（常州強力電子新材料製））　　　　　　　　　　　　　　　　　　　　９．０部
溶剤（Ｅ）：プロピレングリコールモノメチルエーテルアセテート
　　　　　　　　　　　　　　　　　　　　　　　　　　　　４８４．２部
レベリング剤（Ｆ）：ポリエーテル変性シリコーンオイル（トーレシリコーンＳＨ８４００；東レ・ダウコーニング（株）製）　　　　　　　　　　　　　０．１部 (2) Preparation of Colored Curable Resin Composition 1 Colored curable resin composition 1 was obtained by mixing the following components.
Colorant (A): Color dispersion 1 407.1 parts Metal compound (G): Bis(8-quinolinolato)copper(II) 5.3 parts Resin (B): Resin (B-2) obtained in Synthesis Example 3 51.8 parts (solid equivalent) Polymerizable compound (C): (Dipentaerythritol polyacrylate: Trade name A-9550, manufactured by Shin-Nakamura Chemical Co., Ltd.) 42.5 parts (solid equivalent)
Polymerization initiator (D): N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine: Trade name TR-PBG327 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) 9.0 parts Solvent (E): Propylene glycol monomethyl ether acetate 484.2 parts Leveling agent (F): Polyether modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.1 parts
（３）　着色塗膜の作製
　得られた着色硬化性樹脂組成物１を、５ｃｍ角のガラス基板（イーグル２０００；コーニング製）上にスピンコート法で塗布したのち、１００℃で３分間プリベークして光学フィルタを得た。その後、オーブン中、２３０℃で２０分間ポストベークを行い、着色塗膜１を得た。 (3) Preparation of Colored Coating Film The obtained colored curable resin composition 1 was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning) by spin coating, and then prebaked at 100° C. for 3 minutes to obtain an optical filter. Then, postbaked in an oven at 230° C. for 20 minutes to obtain a colored coating film 1.
（４）　耐光性試験
　得られた着色塗膜１上に紫外線カットフィルター（ＣＯＬＯＲＥＤ　ＯＰＴＩＣＡＬ　ＧＬＡＳＳ　Ｌ３８；ホヤ社製；３８０ｎｍ以下の光をカットする）を配置し、大気中、耐光性試験機（ＳＵＮＴＥＳＴ　ＣＰＳ＋：東洋精機社製）にてキセノンランプ光を６７時間照射して、硬化膜１を得た。 (4) Light resistance test An ultraviolet ray cut filter (COLORED OPTICAL GLASS L38; manufactured by Hoya Co., Ltd.; cuts light of 380 nm or less) was placed on the obtained colored coating film 1, and the film was irradiated with xenon lamp light in the atmosphere for 67 hours using a light resistance tester (SUNTEST CPS+; manufactured by Toyo Seiki Co., Ltd.) to obtain a cured film 1.
（５）　吸光度測定
　得られたガラス基板上の硬化膜１について、測色機（ＯＳＰ－ＳＰ－２００；オリンパス（株）製）を用いて耐光性試験前後の吸収分光を測定し、吸光度維持率を求めた。なお本試験での吸光度維持率とは、耐光性試験前の着色塗膜１の極大吸収波長における吸光度を１００％とした値である。吸光度維持率が高いほど耐光性が良いことを意味する。また、着色塗膜１の耐光性が良好であれば、同じ着色硬化性樹脂組成物１から作製された着色パターンも、耐光性は良好であるといえる。結果を表３に示す。 (5) Absorbance Measurement The obtained cured film 1 on the glass substrate was measured for absorption spectroscopy before and after the lightfastness test using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation) to determine the absorbance retention rate. The absorbance retention rate in this test is a value obtained by taking the absorbance at the maximum absorption wavelength of the colored coating film 1 before the lightfastness test as 100%. The higher the absorbance retention rate, the better the lightfastness. Furthermore, if the lightfastness of the colored coating film 1 is good, it can be said that the colored pattern produced from the same colored curable resin composition 1 also has good lightfastness. The results are shown in Table 3.
＜比較例１＞
　実施例１のビス（８－キノリノラト)銅(ＩＩ)を用いないこと以外は、実施例１と同様にして着色硬化性樹脂組成物２を得て、着色塗膜２を作製した。各例の組成及び耐光性試験の結果を表３に示す。 <Comparative Example 1>
A colored curable resin composition 2 was obtained and a colored coating film 2 was produced in the same manner as in Example 1, except that bis(8-quinolinolato)copper(II) of Example 1 was not used. The composition and light resistance test results of each example are shown in Table 3.
Figure JPOXMLDOC01-appb-T000036
Figure JPOXMLDOC01-appb-T000036

Claims (6)

  1. 　着色剤、樹脂、重合開始剤、重合性化合物、及び金属化合物を含み、前記金属化合物が、式（Ｉ）で表される化合物を含むことを特徴とする着色硬化性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     ［式（Ｉ）中、ＲA1～ＲA6は、互いに独立に、水素原子、ハロゲン原子、炭素数１～２０の炭化水素基、ヒドロキシ基、アミノ基、ニトロ基、カルボキシ基、スルホ基、ＯＲA7、ＮＨＲA7、又はＮ(ＲA7)2を表し、ＲA7は、炭素数１～１０の炭化水素基を表す。
    　ＸAは、ハロゲン原子、炭素数１～２０の炭化水素基、ヒドロキシ基、アミノ基、ニトロ基、カルボキシ基、スルホ基、ＯＲA7、ＮＨＲA7、又はＮ(ＲA7)2を表す。
    　ＭAは、第８～１３族金属原子を表し、ｎは、１～３の整数であり、ｍは、０以上の整数であり、ＭAの原子価ａとの間に、ｍ＝ａ－ｎの関係を有し、ＭA及びＮ間の点線は、配位結合を表す。］     A colored curable resin composition comprising a colorant, a resin, a polymerization initiator, a polymerizable compound, and a metal compound, the metal compound comprising a compound represented by formula (I):
    Figure JPOXMLDOC01-appb-C000001
     [In formula (I), R A1 to R A6 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, an amino group, a nitro group, a carboxyl group, a sulfo group, OR A7 , NHR A7 , or N(R A7 ) 2 , where R A7 represents a hydrocarbon group having 1 to 10 carbon atoms.
    X A represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, an amino group, a nitro group, a carboxyl group, a sulfo group, OR A7 , NHR A7 , or N(R A7 ) 2 .
    M A represents a metal atom of Groups 8 to 13, n is an integer of 1 to 3, m is an integer of 0 or more, and has a relationship of m=a-n with the valence a of M A , and the dotted line between M A and N represents a coordinate bond.
  2. 　ＭAが第８～１３族の第４周期の金属原子を表す請求項１に記載の着色硬化性樹脂組成物。 2. The colored curable resin composition according to claim 1, wherein M A represents a metal atom of the 4th period of Groups 8 to 13.
  3. 　ＭAが銅原子である請求項１又は２に記載の着色硬化性樹脂組成物。 3. The colored curable resin composition according to claim 1, wherein M A is a copper atom.
  4. 　着色剤が、式（ＩＩ）で表される化合物を含む請求項１又は２に記載の着色硬化性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000002
     ［式（ＩＩ）中、Ｒ1～Ｒ4は、互いに独立に、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又は置換基を有していてもよい炭素数６～２０の１価の芳香族炭化水素基を表し、該飽和炭化水素基に含まれる－ＣＨ2－は、－Ｏ－、－ＣＯ－又は－ＮＲ11－で置き換わっていてもよい。Ｒ1及び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及びＲ4は、一緒になって窒素原子を含む環を形成してもよい。
    　Ｒ5は、－ＯＨ、－ＳＯ3 -、－ＳＯ3Ｈ、－ＳＯ3 -Ｚ+、－ＣＯ2Ｈ、－ＣＯ2 -Ｚ+、－ＣＯ2Ｒ8、－ＳＯ3Ｒ8又は－ＳＯ2ＮＲ9Ｒ10を表す。
    　Ｒ6及びＲ7は、互いに独立に、水素原子又は炭素数１～６のアルキル基を表す。
    　ｍは、０～５の整数を表す。ｍが２以上のとき、複数のＲ5は同一でも異なってもよい。
    　ａは、０又は１の整数を表す。
    　Ｘは、ハロゲン原子を表す。
    　Ｚ+は、+Ｎ（Ｒ11）4、Ｎａ+又はＫ+を表し、４つのＲ11は同一でも異なってもよい。
    　Ｒ8は、炭素数１～２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
    　Ｒ9及びＲ10は、互いに独立に、水素原子又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、該飽和脂肪族炭化水素基に含まれる－ＣＨ2－は、－Ｏ－、－ＣＯ－、－ＮＨ－又は－ＮＲ8－で置き換っていてもよく、Ｒ9及び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い。
    　Ｒ11は、水素原子、炭素数１～２０の１価の飽和炭化水素基又は炭素数７～１０のアラルキル基を表す。］     The colored curable resin composition according to claim 1 or 2, wherein the colorant comprises a compound represented by formula (II):
    Figure JPOXMLDOC01-appb-C000002
     [In formula (II), R 1 to R 4 each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group of 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group of 6 to 20 carbon atoms which may have a substituent, and -CH 2 - contained in the saturated hydrocarbon group may be replaced by -O-, -CO- or -NR 11 -. R 1 and R 2 may be joined together to form a ring containing a nitrogen atom, and R 3 and R 4 may be joined together to form a ring containing a nitrogen atom.]
    R5 represents -OH, -SO3- , -SO3H , -SO3 - Z + , -CO2H , -CO2 - Z + , -CO2R8 , -SO3R8 or -SO2NR9R10 .
    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 of 0 to 5. When m is 2 or more, multiple R5's may be the same or different.
    a represents an integer of 0 or 1.
    X represents a halogen atom.
    Z + represents + N(R 11 ) 4 , Na + or K + , and the four R 11 s may be the same or different.
    R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
    R 9 and R 10 each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, in which -CH 2 - contained in the saturated aliphatic hydrocarbon group may be replaced by -O-, -CO-, -NH- or -NR 8 -, and R 9 and R 10 may bond to each other to form a 3- to 10-membered heterocycle containing a nitrogen atom.
    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.
  5. 　請求項１又は２に記載の着色硬化性樹脂組成物から形成される光学フィルタ。 An optical filter formed from the colored curable resin composition according to claim 1 or 2.
  6. 　請求項５に記載の光学フィルタを含む固体撮像素子。 A solid-state imaging device including the optical filter according to claim 5.
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