WO2023037995A1 - Colored curable composition - Google Patents

Colored curable composition Download PDF

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Publication number
WO2023037995A1
WO2023037995A1 PCT/JP2022/033227 JP2022033227W WO2023037995A1 WO 2023037995 A1 WO2023037995 A1 WO 2023037995A1 JP 2022033227 W JP2022033227 W JP 2022033227W WO 2023037995 A1 WO2023037995 A1 WO 2023037995A1
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Prior art keywords
group
formula
carbon atoms
hydrocarbon group
optionally substituted
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PCT/JP2022/033227
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French (fr)
Japanese (ja)
Inventor
智博 中山
拓磨 青木
Original Assignee
住友化学株式会社
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Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to CN202280060111.4A priority Critical patent/CN117916326A/en
Priority to KR1020247005199A priority patent/KR20240054974A/en
Publication of WO2023037995A1 publication Critical patent/WO2023037995A1/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
    • C08K5/10—Esters; Ether-esters
    • 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
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-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
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • 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
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
    • C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
    • 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
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029

Definitions

  • the present invention relates to a colored curable composition.
  • Color filters used in display devices such as liquid crystal display devices, electroluminescence display devices and plasma displays, and solid-state imaging devices such as CCD and CMOS sensors are manufactured from colored curable compositions.
  • Colored curable compositions contain various colorants, and for example, colored curable compositions containing phthalocyanine compounds are known (Patent Documents 1 and 2).
  • the present invention provides a colored curable composition in which the line width change rate of the pattern obtained is small even when the colored curable composition after storage is used, that is, even after storage
  • An object of the present invention is to provide a colored curable composition with good pattern stability.
  • the present invention includes the following inventions. [1] containing a coloring agent, a resin, a polymerizable compound, a polymerization initiator, and a carbonate compound, the coloring agent comprises a phthalocyanine compound, The colored curable composition, wherein the polymerization initiator contains an oxime compound. [2] The colored curable composition according to [1], wherein the carbonate compound is a compound represented by formula (I).
  • R 1 and R 2 each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
  • At least one of R 1 and R 2 is an optionally substituted tertiary alkyl group having 4 to 20 carbon atoms, or an optionally substituted C 6 to 20
  • the colored curable composition according to [2] which is an aryl group or an optionally substituted aralkyl group having 7 to 20 carbon atoms.
  • X x1 to X x4 each independently represent -R x4 , -OR x4 , -SR x4 , -SO 3 H, -SO 3 - T + , -SO 3 R x10 , -SO 2 NR x11 R x12 , halogen represents an atom or a nitro group.
  • R x4 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group having 2 to 20 carbon atoms and having —CH 2 — In some cases, the --CH 2 -- may be replaced with --O--, --S-- or --CO--.
  • T + represents + N(R X13 ) 4 or an alkali metal ion, and each R X13 independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • R X10 represents a saturated hydrocarbon group having 1 to 20 carbon atoms.
  • R X11 and R X12 each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
  • nx1 to nx4 each independently represent an integer of 0 to 4;
  • M 1 represents a metal atom, a metal oxide, a metal hydroxide, a metal halide, a phosphorus-containing group-bonded metal, a silicon-containing group-bonded metal, an oxycarbonyl-containing group-bonded metal, or an oxysulfonyl-containing group-bonded metal.
  • X x1 to X x4 and nx1 to nx4 are the same as above.
  • M 2 and M 3 each independently represent a metal atom, metal oxide, metal hydroxide, or metal halide.
  • R a6 to R a12 each independently represent a hydrogen atom, a hydroxy group, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted C 1 to represents 20 heterocyclic groups, and R a6 and R a7 , R a8 and R a9 , or R a10 and R a11 may combine with each other to form a ring;
  • the hydrocarbon group has 2 to 20 carbon atoms and has —CH 2 —
  • the —CH 2 — may be replaced with —O—, —S— or —CO—. good.
  • X x5 to X x12 each independently represent -R x5 , -OR x5 , -SR x5 , -SO 3 H, -SO 3 - Q + , -SO 3 R x14 , -SO 2 NR x15 R x16 , halogen represents an atom or a nitro group.
  • R x5 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group having 2 to 20 carbon atoms, and the hydrocarbon group having —CH 2 — In some cases, the --CH 2 -- may be replaced with --O--, --S-- or --CO--.
  • Q + represents + N(R X17 ) 4 or an alkali metal ion
  • each R X17 independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • R X14 represents a saturated hydrocarbon group having 1 to 20 carbon atoms.
  • R X15 and R X16 each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
  • nx5 to nx12 each independently represent an integer of 0 to 4; ] [5]
  • the colored curable composition according to any one of [1] to [4], wherein the phthalocyanine compound is a compound represented by Formula (Xa) or Formula (Xb).
  • R a1 to R a5 and R a13 to R a14 each independently have a hydrogen atom, a hydroxy group, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. any two of R a1 and R a2 or R a3 to R a5 may combine with each other to form a ring.
  • R x1 represents an optionally substituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms
  • R x2 represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or a single bond connecting Z x2 and R x1 .
  • Z x1 and Z x2 each independently represent a single bond or an oxygen atom.
  • X x1 to X x4 and nx1 to nx4 are the same as above.
  • R x3 represents an optionally substituted C 2-20 aliphatic unsaturated hydrocarbon group or an optionally substituted C 6-20 aromatic hydrocarbon group.
  • Z x3 represents a single bond or an oxygen atom.
  • X x5 to X x12 and nx5 to nx12 are the same as above.
  • [7] A color filter formed from the colored curable composition according to any one of [1] to [6].
  • [8] A display device including the color filter of [7].
  • a solid-state imaging device including the color filter according to [7].
  • the present invention includes a coloring agent (hereinafter sometimes referred to as a coloring agent (A)), a resin (hereinafter sometimes referred to as a resin (B)), a polymerizable compound (hereinafter sometimes referred to as a polymerizable compound (C) ), a polymerization initiator (hereinafter sometimes referred to as a polymerization initiator (D)), and a carbonate compound (hereinafter sometimes referred to as a carbonate compound (E)), and the coloring agent (A) is a phthalocyanine compound and wherein the polymerization initiator (D) includes a colored curable composition containing an oxime compound.
  • a coloring agent hereinafter sometimes referred to as a coloring agent (A)
  • a resin hereinafter sometimes referred to as a resin (B)
  • a polymerizable compound hereinafter sometimes referred to as a polymerizable compound (C)
  • a polymerization initiator hereinafter sometimes referred to as a polymer
  • the colored curable composition of the present invention may contain a leveling agent (hereinafter sometimes referred to as leveling agent (F)).
  • the colored curable composition of the present invention may contain a solvent (hereinafter sometimes referred to as solvent (G)).
  • solvent hereinafter sometimes referred to as solvent (G)
  • the compounds exemplified as each component can be used singly or in combination unless otherwise specified.
  • the colored curable composition according to the present invention contains a phthalocyanine compound as a coloring agent.
  • a phthalocyanine compound include compounds represented by the following formulas (X1) to (X3).
  • the present invention will be described more specifically with partial structures of the compounds represented by formulas (X1) to (X3). Definitions common to Formula (Xa), Formula (Xb), Formula (X0), Formula (XI), Formula (XII), Formula (YI) or Formula (YII) will be described later.
  • X x1 to X x4 each independently represent -R x4 , -OR x4 , -SR x4 , -SO 3 H, -SO 3 - T + , -SO 3 R x10 , -SO 2 NR x11 R x12 , halogen represents an atom or a nitro group.
  • R x4 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group having 2 to 20 carbon atoms and having —CH 2 — In some cases, the --CH 2 -- may be replaced with --O--, --S-- or --CO--.
  • T + represents + N(R X13 ) 4 or an alkali metal ion, and each R X13 independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • R X10 represents a saturated hydrocarbon group having 1 to 20 carbon atoms.
  • R X11 and R X12 each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
  • nx1 to nx4 each independently represent an integer of 0 to 4;
  • M 1 represents a metal atom, a metal oxide, a metal hydroxide, a metal halide, a phosphorus-containing group-bonded metal, a silicon-containing group-bonded metal, an oxycarbonyl-containing group-bonded metal, or an oxysulfonyl-containing group-bonded metal.
  • X x1 to X x4 and nx1 to nx4 are the same as above.
  • M 2 and M 3 each independently represent a metal atom, metal oxide, metal hydroxide, or metal halide.
  • R a6 to R a12 each independently represent a hydrogen atom, a hydroxy group, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted C 1 to represents 20 heterocyclic groups, and R a6 and R a7 , R a8 and R a9 , or R a10 and R a11 may combine with each other to form a ring;
  • the hydrocarbon group has 2 to 20 carbon atoms and has —CH 2 —
  • the —CH 2 — may be replaced with —O—, —S— or —CO—. good.
  • X x5 to X x12 each independently represent -R x5 , -OR x5 , -SR x5 , -SO 3 H, -SO 3 - Q + , -SO 3 R x14 , -SO 2 NR x15 R x16 , halogen represents an atom or a nitro group.
  • R x5 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group having 2 to 20 carbon atoms, and the hydrocarbon group having —CH 2 — In some cases, the --CH 2 -- may be replaced with --O--, --S-- or --CO--.
  • Q + represents + N(R X17 ) 4 or an alkali metal ion
  • each R X17 independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • R X14 represents a saturated hydrocarbon group having 1 to 20 carbon atoms.
  • R X15 and R X16 each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
  • nx5 to nx12 each independently represent an integer of 0 to 4; ]
  • Specific metal atoms represented by M 1 to M 3 include Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, and the like. Among them, Cu, Ni, Zn, or Al is particularly preferable.
  • metal oxides represented by M 1 to M 3 specifically, VO, GeO and the like are preferably mentioned.
  • Specific preferred metal hydroxides represented by M 1 to M 3 include AlOH, Si(OH) 2 , Cr(OH) 2 and Sn(OH) 2 .
  • metal halides represented by M 1 to M 3 include AlCl, SiCl 2 , VCl, VCl 2 , VOCl, FeCl, GaCl and ZrCl.
  • the phosphorus-containing group-bonded metal represented by M 1 has a structure in which a group containing a phosphorus atom is bonded to a metal atom .
  • Examples of the metal atom represented by are those described above.
  • the silicon-containing group-bonded metal represented by M 1 has a structure in which a silicon-containing group is bonded to a metal atom .
  • the metal atom represented by are those described above.
  • the silicon-containing group is preferably a group represented by --O--SiR a3 R a4 R a5 .
  • the oxycarbonyl-containing group-bonded metal represented by M 1 has a structure in which an oxycarbonyl-containing group is bonded to a metal atom.
  • Examples of the metal atom represented by M 3 include those described above.
  • the oxysulfonyl-containing group-bonded metal represented by M 1 has a structure in which an oxysulfonyl-containing group is bonded to a metal atom.
  • Examples of the metal atom represented by M 3 include those described above.
  • M 2 and M 3 may be the same or different, but are preferably the same.
  • M 2 and M 3 are each independently preferably Cu, Ni, Zn or Al; oxides thereof; hydroxides thereof; halides thereof; More preferably, they are Cu, Ni, Zn or Al each independently.
  • the phthalocyanine compound contained as the coloring agent of the present invention is preferably an aluminum phthalocyanine compound.
  • An aluminum phthalocyanine compound is a compound having a phthalocyanine skeleton and forming a complex between the phthalocyanine skeleton and aluminum.
  • the aluminum phthalocyanine compound is preferably a compound represented by Formula (Xa) or Formula (Xb).
  • R a1 to R a5 and R a13 to R a14 each independently have a hydrogen atom, a hydroxy group, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or a substituent; any two of R a1 and R a2 or R a3 to R a5 may combine to form a ring.
  • X x1 to X x4 and nx1 to nx4 are the same as above.
  • L, X x5 to X x12 and nx5 to nx12 are the same as above.
  • R a1 is preferably -R b1 , -OR b1 , -SR b1 or -CO-R b1 .
  • R a2 is preferably -R b2 , -OR b2 , -SR b2 or -CO-R b2 .
  • R b1 and R b2 represent optionally substituted hydrocarbon groups having 1 to 20 carbon atoms, and R b1 and R b2 may combine with each other to form a ring.
  • R a12 is preferably -R b3 , -OR b3 , -SR b3 or -CO-R b3 .
  • R b3 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
  • the compound represented by formula (Xa) is preferably a compound represented by formula (X0) or formula (XI).
  • the compound represented by the formula (Xb) is preferably a compound represented by the formula (XII).
  • the present invention will be described more specifically with partial structures of the compounds represented by formula (X0), formula (XI), or formula (XII).
  • R x1 represents an optionally substituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms
  • R x2 represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or a single bond connecting Z x2 and R x1 .
  • Z x1 and Z x2 each independently represent a single bond or an oxygen atom.
  • X x1 to X x4 and nx1 to nx4 are the same as above.
  • R x3 represents an optionally substituted C 2-20 aliphatic unsaturated hydrocarbon group or an optionally substituted C 6-20 aromatic hydrocarbon group.
  • Z x3 represents a single bond or an oxygen atom.
  • X x5 to X x12 and nx5 to nx12 are the same as above. ]
  • the phthalocyanine compound is also preferably a compound represented by formula (YI) or formula (YII).
  • YI a compound represented by formula (YI) or formula (YII).
  • the present invention will be described more specifically with partial structures of the compounds represented by formula (YI) or formula (YII).
  • R y1 represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
  • R y2 represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or a single bond connecting Z y3 and R y1 .
  • Y 1 and Z y1 each independently represent an oxygen atom or a sulfur atom.
  • Zy2 and Zy3 each independently represent a single bond, an oxygen atom or a sulfur atom. However, at least one of Y1 , Zy1 , Zy2 and Zy3 represents a sulfur atom.
  • X y1 to X y4 each independently represent -R y4 , -OR y4 , -SR y4 , -SO 3 H, -SO 3 - M + , -SO 3 R y10 , -SO 2 NR y11 R y12 , halogen represents an atom or a nitro group.
  • R y4 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
  • M + represents + N(R y13 ) 4 or an alkali metal ion, and each R y13 independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • R y10 represents a saturated hydrocarbon group having 1 to 20 carbon atoms.
  • R y11 and R y12 each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
  • ny1 to ny4 each independently represent an integer of 0 to 4;
  • R y3 represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
  • Y2 and Zy4 each independently represent an oxygen atom or a sulfur atom.
  • Zy5 represents a single bond, an oxygen atom or a sulfur atom. However, at least one of Y2 , Zy4 and Zy5 represents a sulfur atom.
  • X y5 to X y12 are each independently -R y5 , -OR y5 , -SR y5 , -SO 3 H, -SO 3 - W + , -SO 3 R y14 , -SO 2 NR y15 R y16 , halogen represents an atom or a nitro group.
  • R y5 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
  • W + represents + N(R y17 ) 4 or an alkali metal ion, and each R y17 independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • R y14 represents a saturated hydrocarbon group having 1 to 20 carbon atoms.
  • R y15 and R y16 each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
  • ny5 to ny12 each independently represent an integer of 0 to 4; ]
  • the compound represented by formula (YI) includes a compound having a resonance structure represented by formula (YIa) or a compound represented by formula (YIb) in equilibrium, and formula (YII)
  • the compound represented by includes a compound having a resonance structure represented by formula (YIIa) or a compound represented by formula (YIIb) having an equilibrium relationship.
  • R y1 , R y2 , Y 1 , Z y1 , Z y2 , Z y3 , X y1 to X y4 and ny1 to ny4 are the same as above.
  • R y3 , Y 2 , Z y4 , Z y5 , X y5 to X y12 and ny5 to ny12 are the same as above.
  • the aliphatic unsaturated hydrocarbon group represented by R x1 and R x3 has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 2 to 7 carbon atoms, and particularly preferably 2 to 5.
  • the aliphatic unsaturated hydrocarbon groups represented by R x1 and R x3 may be chain or cyclic (alicyclic hydrocarbon groups).
  • the unsaturated chain hydrocarbon groups represented by R x1 and R x3 may be linear or branched, and specifically: Ethenyl group (vinyl group), propenyl group (e.g., 1-propenyl group, 2-propenyl group (allyl group)), 1-methylethenyl group, butenyl group (e.g., 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 (e.g., 1-pen
  • Examples of unsaturated alicyclic hydrocarbon groups represented by R x1 and R x3 include: Cycloalkenyl groups such as cyclohexenyl group (e.g., cyclohex-1-en-1-yl group, cyclohex-2-en-1-yl group, cyclohex-3-en-1-yl group), cycloheptenyl group and cyclooctenyl group ; unsaturated polycyclic hydrocarbon groups such as norbornenyl groups; etc.
  • Cycloalkenyl groups such as cyclohexenyl group (e.g., cyclohex-1-en-1-yl group, cyclohex-2-en-1-yl group, cyclohex-3-en-1-yl group), cycloheptenyl group and cyclooctenyl group ; unsaturated polycyclic hydrocarbon groups such as norbornenyl groups; etc.
  • the aliphatic unsaturated hydrocarbon groups having 2 to 20 carbon atoms represented by R x1 and R x3 may have a substituent.
  • Substituents for the aliphatic unsaturated hydrocarbon groups having 2 to 20 carbon atoms represented by R x1 and R x3 include aromatic hydrocarbon groups having 6 to 20 carbon atoms which may be substituted, substituted a heterocyclic group optionally having a group, a halogen atom, a nitro group, a cyano group, —OR xa1 , —CO 2 R xa1 , —SR xa1 , —SO 3 R xa1 , —SO 2 NR xa1 R xa2 and — NR xa1 R xa2 and the like.
  • R xa1 and R xa2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • the hydrocarbon groups having 1 to 20 carbon atoms represented by R xa1 and R xa2 are 1 carbon atoms represented by R b1 to R b3 , R x2 , R x4 , R x5 and R y1 to R y5 described later. ⁇ 20 hydrocarbon groups.
  • the aliphatic unsaturated hydrocarbon group has an aromatic hydrocarbon group as a substituent
  • the total carbon number of the aliphatic unsaturated hydrocarbon group and the aromatic hydrocarbon group as a substituent is 20. It is preferable that:
  • the aromatic hydrocarbon group having 6 to 20 carbon atoms used as a substituent for the unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms represented by R x1 and R x3 includes: phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 4-vinylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, o-tert-butylphenyl group, m-tert-butylphenyl group,
  • the aromatic hydrocarbon group preferably has 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms.
  • the aromatic hydrocarbon group may have a substituent, and examples of the substituent include a halogen atom, a nitro group, a cyano group, —OR xa1 , —CO 2 R xa1 , —SR xa1 and —SO 3 R xa1 . , —SO 2 NR xa1 R xa2 and —NR xa1 R xa2 (provided that R xa1 and R xa2 are the same as above).
  • the heterocyclic group used as a substituent of the unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms represented by R x1 and R x3 may be monocyclic or polycyclic, preferably is a heterocyclic ring containing a heteroatom as a ring member. Heteroatoms include nitrogen, oxygen and sulfur atoms.
  • Heterocyclic rings containing only nitrogen atoms as heteroatoms include monocyclic saturated heterocyclic rings such as aziridine, azetidine, pyrrolidine, piperidine and piperazine; pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4 - Monocyclic unsaturated heterocycles such as 5-membered unsaturated heterocycles such as triazole, 6-membered unsaturated heterocycles such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine; Condensed bicyclic rings such as indoline, isoindoline, isoindoline-1,3-dione, indole, indolizine, benzimidazole, quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, phthalazine, naphthyridine, purine, pteridine, benzopyrazo
  • heterocycles condensed tricyclic heterocycles such as carbazole, acridine, and phenazine;
  • Heterocyclic rings containing only oxygen atoms as heteroatoms include monocyclic saturated heterocyclic rings such as oxirane, oxetane, tetrahydrofuran, tetrahydropyran, 1,3-dioxane and 1,4-dioxane; 1,4-dioxaspiro [4.
  • Bicyclic saturated heterocycles such as decane and 1,4-dioxaspiro[4.5]nonane; Lactone heterocycles such as ⁇ -acetolactone, ⁇ -propiolactone, ⁇ -butyrolactone and ⁇ -valerolactone; monocyclic unsaturated heterocycles such as 5-membered unsaturated heterocyclic rings such as furan, 2H-pyran, 6-membered unsaturated heterocyclic rings such as 4H-pyran; 1-benzofuran, benzopyran, benzodioxole, condensed bicyclic heterocycles such as chroman and isochroman; condensed tricyclic heterocycles such as xanthene and dibenzofuran; and the like.
  • Lactone heterocycles such as ⁇ -acetolactone, ⁇ -propiolactone, ⁇ -butyrolactone and ⁇ -valerolactone
  • monocyclic unsaturated heterocycles such as 5-membered unsaturated
  • the heterocyclic ring containing only a sulfur atom as a heteroatom includes a 5-membered saturated heterocyclic ring such as dithiolane, a monocyclic saturated heterocyclic ring such as a 6-membered saturated heterocyclic ring such as thiane and 1,3-dithiane; monocyclic unsaturated heterocycles such as 5-membered unsaturated heterocycles such as 4H-thiopyran; benzothiopyrans such as benzotetrahydrothiopyran; condensed bicyclic systems such as benzothiophene heterocycles; condensed tricyclic heterocycles such as thianthrene and dibenzothiophene; Heterocyclic rings containing a nitrogen atom and an oxygen atom as heteroatoms include monocyclic saturated heterocyclic rings such as morpholine, 2-pyrrolidone and 2-piperidone; monocyclic unsaturated heterocyclic rings such as oxazole and isoxazole; Condensed bicyclic
  • Heterocyclic rings containing a nitrogen atom and a sulfur atom as heteroatoms include monocyclic unsaturated heterocyclic rings such as thiazole; condensed bicyclic heterocyclic rings such as benzothiazole; condensed tricyclic heterocyclic rings such as phenothiazine; be done.
  • the heterocyclic group preferably has 2 to 30 carbon atoms, more preferably 3 to 22 carbon atoms, and still more preferably 3 to 20 carbon atoms.
  • the heterocyclic group may have a substituent, and examples of the substituent include a halogen atom, a nitro group, a cyano group, —OR xa1 , —CO 2 R xa1 , —SR xa1 , —SO 3 R xa1 , — SO 2 NR xa1 R xa2 and -NR xa1 R xa2 (provided that R xa1 and R xa2 are the same as above).
  • the bonding position of the heterocyclic ring is a portion from which any hydrogen atom contained in each ring is eliminated.
  • Halogen atoms used as substituents of the aliphatic unsaturated hydrocarbon groups having 2 to 20 carbon atoms represented by R x1 and R x3 are exemplified by fluorine, chlorine, bromine and iodine atoms.
  • the aromatic hydrocarbon group represented by R x1 and R x3 has 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, still more preferably 6 to 8 carbon atoms, and particularly preferably 6 carbon atoms.
  • the aromatic hydrocarbon group represented by R x1 and R x3 includes 6 to 20 carbon atoms used as substituents for the aliphatic unsaturated hydrocarbon groups of 2 to 20 carbon atoms represented by R x1 and R x3 . and the aromatic hydrocarbon groups exemplified as the aromatic hydrocarbon groups of .
  • the aromatic hydrocarbon groups having 6 to 20 carbon atoms represented by R x1 and R x3 may have a substituent.
  • substituents of the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R x1 and R x3 include halogen atoms such as fluorine, chlorine, bromine and iodine atoms, nitro group, cyano group, -OR xa1 , —CO 2 R xa1 , —SR xa1 , —SO 3 R xa1 , —SO 2 NR xa1 R xa2 and —NR xa1 R xa2 (provided that R xa1 and R xa2 are the same as above).
  • the number of carbon atoms in the hydrocarbon group represented by is 1 to 20, preferably 1 to 15.
  • the hydrocarbon group having 1 to 20 carbon atoms represented by may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group is saturated or unsaturated. may be linear or cyclic (alicyclic hydrocarbon group).
  • the saturated or unsaturated chain hydrocarbon group represented by methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group , n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group,
  • alkyl group shaped alkyl 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-ethyl propyl group, 3-methylbutyl group, neopentyl group, 1,1-dimethylpropyl group, 1,1,2-trimethylpropyl 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-methylhexyl group, 5-methylhexyl group, 2-ethylhexyl group, 1-methylhexyl group, 1-ethylpentyl group, 1-propyl
  • the number of carbon atoms in the saturated chain hydrocarbon group represented by is preferably 1 to 10, more preferably 1 to 7, and still more preferably 1 to 5.
  • the number of carbon atoms in the unsaturated chain hydrocarbon group represented by is preferably 2 to 10, more preferably 2 to 7, and still more preferably 2 to 5.
  • saturated or unsaturated alicyclic hydrocarbon group represented by cyclopropyl group, 1-methylcyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 1, 2-dimethylcyclohexyl group, 1,3-dimethylcyclohexyl group, 1,4-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,
  • the number of carbon atoms in the saturated or unsaturated alicyclic hydrocarbon group represented by is preferably 3-10.
  • the aromatic hydrocarbon group represented by is an aromatic hydrocarbon having 6 to 20 carbon atoms used as a substituent for the aliphatic unsaturated hydrocarbon groups having 2 to 20 carbon atoms represented by R x1 and R x3 Examples of the group include the aromatic hydrocarbon groups exemplified.
  • the number of carbon atoms in the aromatic hydrocarbon group represented by is preferably 6-20, more preferably 6-10, still more preferably 6-8.
  • the hydrocarbon group represented by is a combination of the above-listed hydrocarbon groups (e.g., an aromatic hydrocarbon group and at least one of an aromatic hydrocarbon group, a chain hydrocarbon group and an alicyclic hydrocarbon group) may be a base, benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2-ethylphenyl) methyl group, (3-ethylphenyl) methyl group, (4 -ethylphenyl)methyl group, (2-(tert-butyl)phenyl)methyl group, (3-(tert-butyl)phenyl)methyl group, (3-(tert-butyl)phenyl)methyl group, (3-(tert-butyl)phenyl)methyl group, (3-(tert-butyl)phenyl)methyl group, (3-(tert-butyl)phenyl)methyl group, (3-(tert-butyl
  • the group represented by is a combination of the above-mentioned hydrocarbon groups (e.g., a chain hydrocarbon group and an alicyclic hydrocarbon group), such as a cyclopropylmethyl group, a cyclopropylethyl group, a cyclobutylmethyl cyclobutylethyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclohexylmethyl group, (2-methylcyclohexyl)methyl group, cyclohexylethyl group, adamantylmethyl group, etc. It may be an alkyl group.
  • R x4 and R x5 When the hydrocarbon group represented by R a1 to R a14 , R x4 and R x5 has 2 to 20 carbon atoms and the hydrocarbon group has —CH 2 —, the —CH 2 — is —O -, -S- or -CO- may be substituted. However, in the hydrocarbon group having 2 to 20 carbon atoms, adjacent —CH 2 — are not simultaneously substituted with —O— and/or —S—, and the terminal —CH 2 — is —O—, -S- or -CO- is never substituted.
  • a plurality of —CH 2 — substitutable hydrocarbon groups having 1 to 20 carbon atoms exist, the number of substitutions is not necessarily limited to one.
  • two —CH 2 — in a hydrocarbon group having 4 carbon atoms are replaced with —O— to give *—O—CH 2 —O—
  • a group in which -CH 2 - in a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with -O-, -S- or -CO-.
  • the hydrocarbon group having 1 to 20 carbon atoms represented by may have a substituent.
  • Substituents for the hydrocarbon group having 1 to 20 carbon atoms represented by may be optionally substituted heterocyclic groups, halogen atoms, nitro groups, cyano groups, —OR xa1 , —CO 2 R xa1 , -SR xa1 , -SO 3 R xa1 , -SO 2 NR xa1 R xa2 and -NR xa1 R xa2 (provided that R xa1 and R xa2 are the same as above).
  • the heterocyclic group used as a substituent of the hydrocarbon group having 1 to 20 carbon atoms represented by may be monocyclic or polycyclic, preferably a heteroatom as a ring constituent is a heterocyclic ring containing Heteroatoms include nitrogen, oxygen and sulfur atoms.
  • heterocyclic ring examples include the same heterocyclic groups used as substituents of aliphatic unsaturated hydrocarbon groups having 2 to 20 carbon atoms represented by R x1 and R x3 .
  • the heterocyclic group preferably has 2 to 30 carbon atoms, more preferably 3 to 22 carbon atoms, and still more preferably 3 to 20 carbon atoms.
  • the heterocyclic group may have a substituent, and examples of the substituent include a halogen atom, a nitro group, a cyano group, —OR xa1 , —CO 2 R xa1 , —SR xa1 , —SO 3 R xa1 , — SO 2 NR xa1 R xa2 and -NR xa1 R xa2 (provided that R xa1 and R xa2 are the same as above).
  • the bonding position of the heterocyclic ring is a portion from which any hydrogen atom contained in each ring is eliminated.
  • halogen atom used as a substituent of the hydrocarbon group having 1 to 20 carbon atoms represented by is exemplified by a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the saturated hydrocarbon groups having 1 to 20 carbon atoms represented by R x10 , R x14 , R y10 and X y14 include R a1 to R a14 , R b1 to R b3 , R x2 , R x4 , R x5 , R Of the hydrocarbon groups represented by x11 to R x13 , R x15 to R x17 , R y1 to R y5 , R y11 to R y13 and R y15 to R y17 , straight-chain alkyl groups and branched-chain alkyl groups , the cycloalkyl group, and the groups exemplified as the saturated polycyclic hydrocarbon group.
  • the heterocyclic group having 1 to 20 carbon atoms represented by R a1 to R a14 may be monocyclic or polycyclic, and is preferably a heterocyclic ring containing a heteroatom as a ring constituent. be. Heteroatoms include nitrogen, oxygen and sulfur atoms. Examples of the heterocyclic ring include the same heterocyclic groups used as substituents of aliphatic unsaturated hydrocarbon groups having 2 to 20 carbon atoms represented by R x1 and R x3 . The heterocyclic group preferably has 3 to 20 carbon atoms.
  • the heterocyclic group may have a substituent, and examples of the substituent include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 10 carbon atoms, —OR xa1 , —CO 2 R xa1 and —SR. xa1 , -SO 3 R xa1 , -SO 2 NR xa1 R xa2 and -NR xa1 R xa2 (provided that R xa1 and R xa2 are the same as above).
  • the bonding position of the heterocyclic ring is a portion from which any hydrogen atom contained in each ring is eliminated.
  • R x1 is an optionally substituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms
  • an unsaturated bond may be formed between the carbon atoms that are members of the ring, and is a member of the ring
  • An unsaturated bond may be formed between a carbon atom and a carbon atom that is not a member of the ring, and an unsaturated bond may be formed between carbon atoms that are not a member of the ring.
  • R y2 is a single bond connecting Z y3 and R y1
  • a ring is formed. That is, when R y2 is a single bond connecting Z y3 and R y1 , any carbon atom in the optionally substituted hydrocarbon group having 1 to 20 carbon atoms represented by R y1 A bond formed by sharing a pair of electrons with Z y3 corresponds to a single bond represented by R y2 .
  • nx1 to nx12 and ny1 to ny12 each independently represent an integer of 0 to 4; nx1 to nx4 may be the same or different, but are preferably the same; nx5 to nx12 may be the same or different, but are preferably the same; ny4 may be the same or different but is preferably the same, and ny5 to ny12 may be the same or different but are preferably the same.
  • nx1 represents an integer of 2 or more
  • multiple X x1 may be the same or different. The same applies to a plurality of X x2 to X x12 and X y1 to X y12 when nx2 to nx12 and ny1 to ny12 represent integers of 2 or more.
  • substitution position of X x1 is not particularly limited, but when nx1 is 1, it is preferably at the 2nd or 3rd position in the following partial structural formula, position is preferred. The same applies to the substitution positions of X x2 to X x12 and X y1 to X y12 .
  • * indicates a bond.
  • Halogen atoms represented by X x1 to X x12 and X y1 to X y12 include fluorine, chlorine, bromine and iodine atoms, preferably fluorine, chlorine or bromine. , more preferably a fluorine atom.
  • -R x4 represented by X x1 to X x4 , -R x5 represented by X x5 to X x12 , -R y4 represented by X y1 to X y4 or -R represented by X y5 to X y12 y5 is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably a saturated chain hydrocarbon group having 1 to 20 carbon atoms, still more preferably a saturated chain hydrocarbon group having 1 to 10 carbon atoms, A branched alkyl group having a number of 1 to 5 is more preferred, and a tert-butyl group is particularly preferred.
  • R X13 , R X17 , R y13 and R y17 are each independently preferably a hydrogen atom or a saturated chain hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom or a saturated chain hydrocarbon group having 1 to 10 carbon atoms. is more preferred, and a hydrogen atom or a saturated chain hydrocarbon group having 1 to 5 carbon atoms is even more preferred.
  • Alkali metal ions represented by T + , Q + , M + , and W + are each independently preferably lithium ion, sodium ion, or potassium ion.
  • the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R x10 , R x14 , R y10 and R y14 is preferably a linear or branched alkyl group having 1 to 20 carbon atoms. ⁇ 10 linear alkyl groups are more preferred.
  • R x11 , R x12 , R x15 , R x16 , R y11 , R y12 , R y15 and R y16 are each independently preferably a hydrogen atom or a saturated chain hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom Alternatively, a saturated chain hydrocarbon group having 1 to 10 carbon atoms is more preferable, and a hydrogen atom or a saturated chain hydrocarbon group having 1 to 5 carbon atoms is more preferable.
  • R x1 is An optionally substituted unsaturated chain hydrocarbon group having 2 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms is preferred, An optionally substituted unsaturated chain hydrocarbon group having 2 to 10 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 8 carbon atoms is more preferable, An optionally substituted unsaturated chain hydrocarbon group having 2 to 7 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 7 carbon atoms is more preferable, optionally substituted ethenyl group, optionally substituted propenyl group, optionally substituted butenyl group, optionally substituted 3-methyl-2 -butenyl group, optionally substituted 3-methyl-1,2-butadienyl group, optionally substituted heptenyl group, optionally substituted ethynyl group, substituent A propynyl group optionally having , a butynyl group optionally having a substitu
  • Rx1 When the aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms represented by R x1 has a substituent, the substituent is preferably a phenyl group.
  • Rx2 is An optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms or an optionally substituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms is preferred.
  • examples of the aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms include the groups described above as the alkenyl group, alkynyl group and unsaturated alicyclic hydrocarbon group.
  • substituents that the C2-C20 aliphatic unsaturated hydrocarbon group may have include C2-C20 aliphatic unsaturated hydrocarbon groups represented by R x1 and R x3 .
  • the groups described as the optional substituents can be mentioned.
  • the total carbon number of the aliphatic unsaturated hydrocarbon group and the aromatic hydrocarbon group as a substituent is 20. It is below.
  • Specific examples of the aliphatic unsaturated hydrocarbon group having an aromatic hydrocarbon group as a substituent include groups exemplified as arylalkenyl groups and arylalkynyl groups.
  • R x2 is An optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms or an unsaturated chain hydrocarbon group having 2 to 20 carbon atoms which may have a substituent (i.e. alkenyl group, alkynyl group) is more preferred, An optionally substituted aromatic hydrocarbon group having 6 to 8 carbon atoms or an optionally substituted unsaturated chain hydrocarbon group having 2 to 7 carbon atoms is more preferable, phenyl group optionally having substituent(s), ethenyl group optionally having substituent(s), propenyl group optionally having substituent(s), butenyl group optionally having substituent(s), substituent 3-methyl-2-butenyl group optionally having a substituent, 3-methyl-1,2-butadienyl group optionally having a substituent, a heptenyl group optionally having a substituent, a substituent An optionally substituted ethynyl group, an optionally substituted propynyl group,
  • the substituent is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, more preferably a phenyl group.
  • X x1 to X x4 are each independently preferably —R x4 or a halogen atom, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, or a halogen atom, and 1 to 5 carbon atoms. is more preferred, and a tert-butyl group, a fluorine atom, a chlorine atom, or a bromine atom is particularly preferred.
  • nx1 to nx4 are each independently, for example, 0 to 2 or 4, preferably 0 to 2, more preferably 0 to 1, still more preferably 0.
  • R x3 is An optionally substituted unsaturated chain hydrocarbon group having 2 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms is preferred, An optionally substituted unsaturated chain hydrocarbon group having 2 to 10 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 8 carbon atoms is more preferable, An optionally substituted unsaturated chain hydrocarbon group having 2 to 5 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 7 carbon atoms is more preferable, optionally substituted ethenyl group, optionally substituted propenyl group, optionally substituted butenyl group, optionally substituted ethynyl group, substituent A propynyl group optionally having , a butynyl group optionally having a substituent, or a phenyl group optionally having a substituent are particularly preferable.
  • the substituent is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, more preferably a phenyl group.
  • X x5 to X x12 are each independently preferably —R x5 or a halogen atom, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, or a halogen atom, and 1 to 5 carbon atoms. is more preferred, and a tert-butyl group, a fluorine atom, a chlorine atom, or a bromine atom is particularly preferred.
  • nx5 to nx12 are each independently, for example, 0 to 2 or 4, preferably 0 to 2, more preferably 0 to 1, still more preferably 0.
  • the phthalocyanine compound contained as the coloring agent of the present invention is It is preferably at least one selected from the group consisting of a compound represented by formula (X1), a compound represented by formula (X2) and a compound represented by formula (X3), C. a compound represented by formula (Xa), a compound represented by formula (Xb), a compound represented by formula (YI), a compound represented by formula (YII); I. Pigment Blue 15, C.I. I. Pigment Blue 15:1, C.I. I. Pigment Blue 15:2, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 15:6, C.I. I. Pigment Blue 16, C.I. I.
  • Pigment Green 7 C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59, C.I. I. Pigment Green 62, and C.I. I. It is more preferably at least one selected from the group consisting of Pigment Green 63, C. a compound represented by formula (X0), a compound represented by formula (XI), a compound represented by formula (XII); I. Pigment Blue 15, C.I. I. Pigment Blue 15:1, C.I. I. Pigment Blue 15:2, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 15:6, C.I. I. Pigment Blue 16, C.I.
  • I. Pigment Green 7 C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59, C.I. I. Pigment Green 62, and C.I. I. It is more preferably at least one selected from the group consisting of Pigment Green 63, It is more preferably at least one selected from the group consisting of the compound represented by formula (X0), the compound represented by formula (XI), and the compound represented by formula (XII).
  • R x1 , R x2 , Z x1 and Z x2 are the same as above. ]
  • Examples of compounds represented by formula (XIA) include compounds represented by formulas (XIA-1) to (XIA-190) shown in Tables 1 to 4.
  • Examples of compounds represented by formula (XIB) include compounds represented by formulas (XIB-1) to (XIB-190) shown in Tables 5 to 8.
  • Examples of compounds represented by formula (XIC) include compounds represented by formulas (XIC-1) to (XIC-190) shown in Tables 9 to 12.
  • Examples of compounds represented by formula (XID) include compounds represented by formulas (XID-1) to (XID-190) shown in Tables 13 to 16.
  • Examples of compounds represented by formula (XIE) include compounds represented by formulas (XIE-1) to (XIE-190) shown in Tables 17 to 20.
  • R x6 and R x7 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent
  • Examples of the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent include substituents represented by R b1 to R b3 , R x2 , R x4 , R x5 and R y1 to R y5 .
  • R x6 and R x7 are each independently preferably a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. * represents a bond.
  • Formula (XIA-1) ⁇ Formula (XIA-12), Formula (XIA-91) ⁇ Formula (XIA-102), Formula (XIA-103) ⁇ Formula (XIA-108), Formula (XIA-115) ⁇ Formula (XIA-119), Formula (XIA-126) ⁇ Formula (XIA-129), Formula (XIA-136) ⁇ Formula (XIA-138), Formula (XIA-145) ⁇ Formula (XIA-146), Formula ( XIA-153), compounds represented by formulas (XIA-181) to (XIA-190) are preferred, Formula (XIA-1) ⁇ Formula (XIA-12), Formula (XIA-103) ⁇ Formula (XIA-105), Formula (XIA-115) ⁇ Formula (XIA-116), Formula (XIA-126), Formula (XIA-136) ⁇ formula (XIA-138), formula (XIA-145) ⁇ formula (XIA-146), formula (
  • Formula (XIC-1) As the compound represented by the formula (XIC), Formula (XIC-1) ⁇ Formula (XIC-12), Formula (XIC-91) ⁇ Formula (XIC-102), Formula (XIC-103) ⁇ Formula (XIC-108), Formula (XIC-115) ⁇ Formula (XIC-119), Formula (XIC-126) ⁇ Formula (XIC-129), Formula (XIC-136) ⁇ Formula (XIC-138), Formula (XIC-145) ⁇ Formula (XIC-146), Formula ( XIC-153), compounds represented by formulas (XIC-181) to (XIC-190) are preferred, Formula (XIC-1) ⁇ Formula (XIC-12), Formula (XIC-103) ⁇ Formula (XIC-105), Formula (XIC-115) ⁇ Formula (XIC-116), Formula (XIC-126) is more preferred, Compounds represented by formula (XIC-1) and formula (XIC-115) are more preferred.
  • Formula (XIE-1) As the compound represented by the formula (XIE), Formula (XIE-1) ⁇ Formula (XIE-12), Formula (XIE-91) ⁇ Formula (XIE-102), Formula (XIE-103) ⁇ Formula (XIE-108), Formula (XIE-115) ⁇ Formula (XIE-119), Formula (XIE-126) ⁇ Formula (XIE-129), Formula (XIE-136) ⁇ Formula (XIE-138), Formula (XIE-145) ⁇ Formula (XIE-146), Formula ( XIE-153), compounds represented by formulas (XIE-181) to (XIE-190) are preferred, Formula (XIE-1) ⁇ Formula (XIE-12), Formula (XIE-103) ⁇ Formula (XIE-105), Formula (XIE-115) ⁇ Formula (XIE-116), Formula (XIE-126) is more preferred, Compounds represented by formula (XIE-1) and formula (XIE-115) are more preferred.
  • Examples of compounds represented by formula (XIIA) include compounds represented by formulas (XIIA-1) to (XIIA-18) shown in Table 21.
  • Examples of compounds represented by formula (XIIB) include compounds represented by formulas (XIIB-1) to (XIIB-18) shown in Table 22.
  • Examples of compounds represented by formula (XIIC) include compounds represented by formulas (XIIC-1) to (XIIC-18) shown in Table 23.
  • Examples of compounds represented by formula (XIID) include compounds represented by formulas (XIID-1) to (XIID-18) shown in Table 24.
  • Examples of compounds represented by formula (XIIE) include compounds represented by formulas (XIIE-1) to (XIIE-18) shown in Table 25.
  • the symbols described in the “R x3 ” columns in Tables 21 to 25 correspond to groups represented by formulas (xiii-1) to (xiii-9). * represents a bond.
  • the compound represented by formula (X0) can be produced, for example, by appropriately reacting the compound represented by formula (XIII) with concentrated sulfuric acid.
  • a compound represented by formula (XI) can be produced, for example, by appropriately reacting a compound represented by formula (XIII) with a compound represented by formula (XIV).
  • the compound represented by formula (XII) can be obtained, for example, by appropriately reacting a compound represented by formula (XIIIa), a compound represented by formula (XIIIb), and a compound represented by formula (XV).
  • R x1 , R x2 , Z x1 , Z x2 , X x1 to X x4 and nx1 to nx4 are the same as above.
  • R y1 is An aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent is preferred, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, more preferably an aromatic hydrocarbon group having 6 to 8 carbon atoms which may have a substituent, An optionally substituted phenyl group is particularly preferred.
  • Ry2 is An optionally substituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms is preferred.
  • the aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms in preferred embodiments of R y2 and R y3 described later includes the groups described as the alkenyl group, alkynyl group, and unsaturated alicyclic hydrocarbon group described above. is mentioned.
  • substituents that the C2-C20 aliphatic unsaturated hydrocarbon group may have include C2-C20 aliphatic unsaturated hydrocarbon groups represented by R x1 and R x3 .
  • the groups described as the optional substituents can be mentioned.
  • the total carbon number of the aliphatic unsaturated hydrocarbon group and the aromatic hydrocarbon group as a substituent is 20. It is below.
  • Specific examples of the aliphatic unsaturated hydrocarbon group having an aromatic hydrocarbon group as a substituent include groups exemplified as arylalkenyl groups and arylalkynyl groups.
  • R y2 is Unsaturated chain hydrocarbon groups of 2 to 10 carbon atoms which may have substituents (that is, alkenyl groups and alkynyl groups) or aromatic carbon atoms of 6 to 10 carbon atoms which may have substituents more preferably a hydrogen group
  • substituents that is, alkenyl groups and alkynyl groups
  • aromatic carbon atoms of 6 to 10 carbon atoms which may have substituents more preferably a hydrogen group
  • An optionally substituted unsaturated chain hydrocarbon group having 2 to 7 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 8 carbon atoms is more preferable
  • An optionally substituted alkenyl group having 2 to 7 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 8 carbon atoms is more preferable
  • An optionally substituted ethenyl group or an optionally substituted phenyl group is particularly preferred.
  • ny1 to ny4 are each independently, for example, 0 to 2 or 4, preferably 0 to 2, more preferably 0 to 1, still more preferably 0.
  • X y1 to X y4 are each independently preferably -R y4 or a halogen atom, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, or a halogen atom, and 1 to 5 carbon atoms. is more preferred, and a tert-butyl group, a fluorine atom, a chlorine atom, or a bromine atom is particularly preferred.
  • At least one of Y 1 , Z y1 , Z y2 and Z y3 represents a sulfur atom, Y 1 is a sulfur atom and Z y1 is an oxygen atom, Y 1 is an oxygen atom and Z y1 is a sulfur atom and Z y2 and Z y3 are sulfur atoms.
  • Zy2 and Zy3 are preferably single bonds.
  • Ry3 is An optionally substituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, An optionally substituted unsaturated chain hydrocarbon group having 2 to 10 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms is more preferable, An optionally substituted unsaturated chain hydrocarbon group having 2 to 7 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 8 carbon atoms is more preferable, An optionally substituted alkenyl group having 2 to 7 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 8 carbon atoms is more preferable, An optionally substituted ethenyl group or an optionally substituted phenyl group is particularly preferred.
  • ny5 to ny12 are each independently, for example, 0 to 2 or 4, preferably 0 to 2, more preferably 0 to 1, still more preferably 0.
  • X y5 to X y12 are each independently preferably -R y5 or a halogen atom, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, or a halogen atom, and 1 to 5 carbon atoms. is more preferred, and a tert-butyl group, a fluorine atom, a chlorine atom, or a bromine atom is particularly preferred.
  • At least one of Y2 , Zy4 and Zy5 represents a sulfur atom. However, when R y3 is an unsaturated aliphatic hydrocarbon group, Z y5 is preferably a single bond.
  • Compounds represented by formula (YI) include compounds represented by formulas (YIA) to (YIE).
  • Examples of the compound represented by formula (YIA) include compounds represented by formulas (YIA-1) to (YIA-24) shown in Table 26.
  • Examples of the compound represented by formula (YIB) include compounds represented by formulas (YIB-1) to (YIB-24) shown in Table 27.
  • Examples of the compound represented by formula (YIC) include compounds represented by formulas (YIC-1) to (YIC-24) shown in Table 28.
  • Examples of the compound represented by formula (YID) include compounds represented by formulas (YID-1) to (YID-24) shown in Table 29.
  • Examples of the compound represented by formula (YIE) include compounds represented by formulas (YIE-1) to (YIE-24) shown in Table 30. In Tables 26 to 30, "yi-1" represents a phenyl group, and "yi-2" represents an ethenyl group.
  • Formula (YIA) As the compound represented by the formula (YIA), Formula (YIA-1) ⁇ Formula (YIA-6), Formula (YIA-13) ⁇ Formula (YIA-18), Formula (YIA-21), Formula (YIA-22) ⁇ Formula (YIA-24) are preferred, Compounds represented by formula (YIA-1), formula (YIA-13), formula (YIA-21), formula (YIA-23) and formula (YIA-24) are more preferred.
  • Formula (YIB) As the compound represented by the formula (YIB), Formula (YIB-1) ⁇ Formula (YIB-6), Formula (YIB-13) ⁇ Formula (YIB-18), Formula (YIB-21), Formula (YIB-22) ⁇ Formula (YIB-24) are preferred, Compounds represented by formula (YIB-1), formula (YIB-13), formula (YIB-21), formula (YIB-23) and formula (YIB-24) are more preferred.
  • Formula (YIC-1) ⁇ Formula (YIC-6), Formula (YIC-13) ⁇ Formula (YIC-18), Formula (YIC-21), Formula (YIC-22) ⁇ Formula (YIC-24) are preferred, Compounds represented by formula (YIC-1), formula (YIC-13), formula (YIC-21), formula (YIC-23) and formula (YIC-24) are more preferred.
  • Formula (YID-1) ⁇ Formula (YID-6), Formula (YID-13) ⁇ Formula (YID-18), Formula (YID-21), Formula (YID-22) ⁇ Formula (YID-24) are preferred, Compounds represented by formula (YID-1), formula (YID-13), formula (YID-21), formula (YID-23) and formula (YID-24) are more preferred.
  • Formula (YIE-1) ⁇ Formula (YIE-6), Formula (YIE-13) ⁇ Formula (YIE-18), Formula (YIE-21), Formula (YIE-22) ⁇ Formula (YIE-24) are preferred, Compounds represented by Formula (YIE-1), Formula (YIE-13), Formula (YIE-21), Formula (YIE-23) and Formula (YIE-24) are more preferred.
  • Compounds represented by formula (YII) include compounds represented by formulas (YIIA) to (YIIE).
  • Compounds represented by formula (YIIA) include, for example, formula (YIIA-1) shown in Table 31 to the compound represented by the formula (YIIA-13).
  • Examples of the compound represented by formula (YIIB) include compounds represented by formulas (YIIB-1) to (YIIB-13) shown in Table 32.
  • Examples of the compound represented by formula (YIIC) include compounds represented by formulas (YIIC-1) to (YIIC-13) shown in Table 33.
  • Examples of the compound represented by the formula (YIID) include compounds represented by the formulas (YIID-1) to (YIID-13) shown in Table 34.
  • Examples of the compound represented by formula (YIIE) include compounds represented by formulas (YIIE-1) to (YIIE-13) shown in Table 35. In Tables 31 to 35, "yi-1" represents a phenyl group and "yi-2" represents an ethenyl group.
  • the compound represented by formula (YI) can be produced, for example, by appropriately reacting a compound represented by formula (YIII) with a compound represented by formula (YIV). Further, the compound represented by the formula (YII) can be produced, for example, by appropriately reacting the compounds represented by the formulas (YIIIa) and (YIIIb) with the compound represented by the formula (YV).
  • R y1 , R y2 , Y 1 , Z y1 , Z y2 , Z y3 , X y1 to X y4 and ny1 to ny4 are the same as above.
  • the phthalocyanine compound can be dispersed uniformly in the dispersant solution by adding a dispersant and performing a dispersion treatment.
  • the phthalocyanine compound may be subjected to dispersion treatment alone, or may be mixed with a plurality of types and subjected to dispersion treatment.
  • the same as the pigment dispersant described later can be used.
  • the amount used is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 15 parts by mass or more and 180 parts by mass or less, and even more preferably, relative to 100 parts by mass of the phthalocyanine compound in the dispersion. is 20 parts by mass or more and 160 parts by mass or less.
  • the amount of the dispersant used is within the above range, there is a tendency to obtain a more uniformly dispersed liquid dispersion.
  • the content of the phthalocyanine compound is preferably 0.5 to 70% by mass, more preferably 1 to 55% by mass, still more preferably 2 to 50% by mass, based on the total solid content of the colored curable composition. Also, the content of the phthalocyanine compound may be 10 to 50% by mass based on the total solid content of the colored curable composition.
  • total amount of solids refers to the total amount of components of the colored curable composition of the present invention excluding the solvent. The total amount of solids and the content of each component relative thereto can be measured by known analysis means such as liquid chromatography and gas chromatography.
  • the content of the phthalocyanine compound is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and even more preferably 10% by mass, based on the total amount of the colorant (A). above, and particularly preferably at least 50% by mass.
  • the upper limit of the content is not particularly limited, but may be 100% by mass, 80% by mass, 70% by mass, or 60% by mass.
  • the coloring agent (A) may further contain a coloring agent different from the phthalocyanine compound (hereinafter sometimes referred to as coloring agent (A2)).
  • the coloring agent (A2) may be either a dye or a pigment, or a mixture thereof.
  • Dyes include, for example, compounds classified as having hues other than pigments in the Color Index (published by The Society of Dyers and Colourists), and known dyes listed in Stain Note (Shikisensha). be done.
  • dyes examples include azo dyes, cyanine dyes, triphenylmethane dyes, thiazole dyes, oxazine dyes, quinophthalone dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, Coumarin dyes, quinoline dyes, nitro dyes, and the like may be used, and known dyes are used.
  • dyes include C.I. I. Solvent Yellow 4 (hereinafter, the description of C.I. Solvent Yellow is omitted and only the number is described. The same applies to others.), 14, 15, 23, 24, 38, 62, 63, 68, 82 , 94, 99, 117, 162, 163, 167, 189; C. I. Solvent Red 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247; C. I. Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86; C. I.
  • C. I. C.I. I. solvent dyes C. I.
  • I. direct dye C. I. Disperse Yellow 51, 54, 76; C. I. Disperse Violet 26, 27; C. I. C.I. I. disperse dyes, 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 Green 1 and other C.I. I. basic dye, C. I.
  • pigments examples include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colorists), and the following pigments can be exemplified.
  • Yellow pigment C.I. 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, etc.
  • Orange pigment C.I. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, etc.
  • Red pigment C.I. I.
  • Purple pigment C.I. I. Pigment Violet 19, 23, 29, 32, 36, 38, etc.
  • one type of pigment or a plurality of pigments may be used for each color, and pigments of each color may be combined.
  • the pigment is subjected to rosin treatment, surface treatment using a pigment derivative into which an acidic or basic group has been introduced, graft treatment to the pigment surface with a polymer compound, etc., atomization by a sulfuric acid atomization method, etc. Treatment, washing treatment with an organic solvent or water for removing impurities, removal treatment by an ion exchange method for ionic impurities, or the like may be performed. It is preferable that the particle size of the pigment is substantially uniform.
  • the pigment can be dispersed uniformly in the dispersant solution by adding a pigment dispersant and performing a dispersion treatment.
  • the pigments may be subjected to dispersion treatment alone, or may be dispersed by mixing plural kinds of pigments.
  • pigment dispersants examples include surfactants, which may be cationic, anionic, nonionic or amphoteric surfactants. Specific examples include surfactants such as polyester-based, polyamine-based and acrylic-based surfactants. These dispersants may be used alone or in combination of two or more.
  • KP manufactured by Shin-Etsu Chemical Co., Ltd.
  • Floren manufactured by Kyoeisha Chemical Co., Ltd.
  • Solsperse registered trademark
  • EFKA registered trademark
  • the amount used is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 15 parts by mass or more and 180 parts by mass or less, and still more preferably 100 parts by mass of the pigment in the dispersion. is 20 parts by mass or more and 160 parts by mass or less.
  • the amount of the pigment dispersant used is within the above range, there is a tendency to obtain a dispersion with a more uniform dispersion state.
  • the content of the colorant (A2) is preferably 1 to 99% by mass, more preferably 1 to 80% by mass, based on the total amount of the colorant (A). , more preferably 20 to 50% by mass.
  • the content of the colorant (A2) may be 20 to 97% by mass, 30 to 95% by mass, or 40 to 90% by mass in the total amount of the colorant (A). good,
  • the content of the coloring agent (A) in the colored curable composition is preferably 0.5 to 80% by mass, more preferably 5 to 70% by mass, more preferably 10 to 55% by mass, based on the total amount of solids. % by mass.
  • the content of the coloring agent (A) is within the above range, it becomes easier to obtain the desired spectrum and color density.
  • the resin (B) is not particularly limited, it is preferably an alkali-soluble resin.
  • the resin (B) include the following resins [K1] to [K6].
  • Resin [K1] at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter sometimes referred to as "(a)"), and a cyclic ether having 2 to 4 carbon atoms
  • a copolymer with a monomer (b) having a structure and an ethylenically unsaturated bond hereinafter sometimes referred to as "(b)”
  • Resin [K2]; (a) and (b), and monomer (c) copolymerizable with (a) (but different from (a) and (b)) hereinafter “(c)” may be called) and a copolymer
  • Resin [K3] copolymer of (a) and (c)
  • (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethyl
  • (b) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (eg, 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 represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as "(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 having an oxetanyl group and an ethylenically unsaturated bond, a monomer (b2) (hereinafter sometimes referred to as “(b2)”), a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)”), etc. mentioned.
  • a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond hereinafter sometimes referred to as "(b1)
  • a monomer having an oxetanyl group and an ethylenically unsaturated bond hereinafter sometimes referred to as "(b2)
  • (b3) monomer having a tetrahydrofuryl group and an
  • (b1) for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as "(b1-1)” ), and a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).
  • (b1-1) includes glycidyl (meth)acrylate, ⁇ -methylglycidyl (meth)acrylate, ⁇ -ethylglycidyl (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(glycidyloxymethyl)styrene , 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxy
  • (b1-2) includes vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (eg, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (eg, Cychromer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (eg, Cychromer M100; manufactured by Daicel Corporation), 3,4-epoxytricyclo [5.2.1. 0 2,6 ]decyl (meth)acrylate, a compound represented by formula (R1), a compound represented by formula (R2), and the like.
  • vinylcyclohexene monoxide eg, 1,2-epoxy-4-vinylcyclohexane (eg, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (eg, Cychromer A400; manufactured by Da
  • R ra and R rb represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group.
  • X ra and X rb represent a single bond, *-R rc -, *-R rc -O-, *-R rc -S- or *-R rc -NH-.
  • R rc represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond with O.
  • alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.
  • Alkyl groups in which hydrogen atoms are substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.
  • R ra and R rb preferably include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.
  • the alkanediyl group includes methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane- A 1,6-diyl group and the like can be mentioned.
  • X ra and X rb are preferably a single bond, a methylene group, an ethylene group, *--CH 2 --O-- and *--CH 2 CH 2 --O--, more preferably a single bond and *--CH 2 CH 2 --O-- (* represents a bond with O).
  • Examples of the compound represented by formula (R1) include compounds represented by any one of formulas (R1-1) to (R1-15). Among them, formula (R1-1), formula (R1-3), formula (R1-5), formula (R1-7), formula (R1-9) or formula (R1-11) to formula (R1-15) A compound represented by is preferable, and a compound represented by formula (R1-1), formula (R1-7), formula (R1-9) or formula (R1-15) is more preferable.
  • Examples of the compound represented by formula (R2) include compounds represented by any one of formulas (R2-1) to (R2-15). Among them, formula (R2-1), formula (R2-3), formula (R2-5), formula (R2-7), formula (R2-9) or formula (R2-11) to formula (R2-15) A compound represented by is preferable, and a compound represented by formula (R2-1), formula (R2-7), formula (R2-9) or formula (R2-15) is more preferable.
  • (b2) is more preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group.
  • (b2) includes 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) is more preferably a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group.
  • Specific examples of (b3) include tetrahydrofurfuryl acrylate (eg, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.
  • (b) is preferably (b1) in that the heat resistance, chemical resistance, etc. of the obtained color filter can be made more reliable. Furthermore, (b1-2) is more preferable in that the storage stability of the colored curable composition is more excellent.
  • (c) includes, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth) Acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 ]Decan-8-yl (meth)acrylate (in the technical field, it is commonly referred to as “dicyclopentanyl (meth)acrylate”.
  • tricyclodecyl (meth)acrylate tricyclo[5.2.1.0 2,6 ]decen-8-yl (meth)acrylate (in the art, it is commonly called “dicyclopentenyl (meth)acrylate”.
  • dicyclopentanyloxyethyl (meth)acrylate dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth) acrylic acid esters such as (meth) acrylate; Hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5- Hydr
  • (c) includes 2-ethylhexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, benzyl (meth)acrylate, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] Hept-2-ene and the like are preferred, and from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2 .2.1]hept-2-ene and the like are more preferred.
  • the ratio of the structural units derived from each of the total structural units constituting the resin [K1] is Structural unit derived from (a); 2 to 60 mol% Structural unit derived from (b); 40 to 98 mol% is preferably Structural unit derived from (a); 10 to 50 mol% Structural unit derived from (b); 50 to 90 mol% is more preferable.
  • the ratio of the structural units of the resin [K1] is within the above range, the storage stability of the colored curable composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter tend to be excellent.
  • the resin [K1] is, for example, the method described in the document "Experimental Methods for Polymer Synthesis” (written by Takayuki Otsu, Published by Kagaku Dojin, 1st Edition, 1st Edition, March 1, 1972) and the document It can be manufactured with reference to the cited document described in .
  • a polymerization initiator e.g., a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and, for example, by replacing oxygen with nitrogen, a deoxygenated atmosphere is created, and while stirring, A method of heating and keeping warm can be mentioned.
  • the polymerization initiator, solvent, and the like used here are not particularly limited, and those commonly used in the relevant 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.).
  • the solvent any solvent can be used as long as it dissolves each monomer, and examples of the solvent (G) include the solvents described later.
  • the obtained copolymer may be used as a solution after the reaction as it is, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. You can use things.
  • the solvent contained in the colored curable composition as a solvent during this polymerization, the solution after the reaction can be used as it is for the preparation of the colored curable composition, so that the colored curable composition
  • the manufacturing process of things can be simplified.
  • the ratio of the structural units derived from each of the total structural units constituting the resin [K2] is Structural unit derived from (a); 2 to 45 mol% Structural unit derived from (b); 2 to 95 mol% Structural unit derived from (c); 1 to 65 mol% is preferably Structural unit derived from (a); 5 to 40 mol% Structural unit derived from (b); 5 to 80 mol% Structural unit derived from (c); 5 to 60 mol% is more preferable.
  • the storage stability of the colored curable composition When the ratio of the structural units of the resin [K2] is within the above range, the storage stability of the colored curable composition, developability when forming a colored pattern, and the solvent resistance and heat resistance of the resulting color filter are improved. It tends to have excellent toughness and mechanical strength.
  • the resin [K2] can be produced, for example, in the same manner as the method for producing the resin [K1].
  • the ratio of the structural units derived from each of the total structural units constituting the resin [K3] is Structural unit derived from (a); 2 to 60 mol% Structural unit derived from (c); 40 to 98 mol% is preferably Structural unit derived from (a); 10 to 50 mol% Structural unit derived from (c); 50 to 90 mol% is more preferable.
  • Resin [K3] can be produced, for example, in the same manner as the method for producing resin [K1].
  • Resin [K4] is a carboxylic acid and/or carboxylic acid anhydride obtained by obtaining a copolymer of (a) and (c), and having (a) a cyclic ether having 2 to 4 carbon atoms possessed by (b). It can be produced by adding to First, a copolymer of (a) and (c) is produced in the same manner as the method for producing resin [K1]. In this case, the ratio of structural units derived from each is preferably the same ratio as mentioned for resin [K3].
  • part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the copolymer is reacted with the cyclic ether having 2 to 4 carbon atoms of (b).
  • the atmosphere in the flask is replaced from nitrogen to air, and (b) a reaction catalyst (e.g., tris ( Dimethylaminomethyl)phenol, triphenylphosphine, etc.) and a polymerization inhibitor (e.g., hydroquinone, metoquinone, etc.) are placed in a flask and reacted at, for example, 60 to 130 ° C. for 1 to 10 hours to obtain a resin [K4 ] can be manufactured.
  • a reaction catalyst e.g., tris ( Dimethylaminomethyl)phenol, triphenylphosphine, etc.
  • a polymerization inhibitor e.g., hydroquinone, metoquinone, etc.
  • the amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By setting it to this range, the storage stability of the colored curable composition, the developability when forming a pattern, and the solvent resistance, heat resistance, mechanical strength and sensitivity of the resulting pattern tend to have a good balance.
  • (b1) is preferable as the (b) used in the resin [K4], and (b1-1) is more preferable.
  • 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 to be used is preferably 0.001 to 5 parts by weight per 100 parts by weight of the total amount of (a), (b) and (c).
  • 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 polymerization, and the like.
  • the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.
  • a copolymer of (b) and (c) is obtained in the same manner as in the method for producing resin [K1] described above.
  • the obtained copolymer may be used as a solution after the reaction as it is, may be used as a concentrated or diluted solution, or may be converted into a solid (powder) by a method such as reprecipitation. You may use what was taken out as.
  • the ratio of structural units derived from (b) and (c) to the total number of moles of all structural units constituting the copolymer is, respectively, Structural unit derived from (b); 5 to 95 mol% Structural unit derived from (c); 5 to 95 mol% is preferably Structural unit derived from (b); 10 to 90 mol% Structural unit derived from (c); 10 to 90 mol% is more preferable.
  • the cyclic ether derived from (b) in the copolymer of (b) and (c) is added to the carboxylic acid or carboxylic anhydride of (a).
  • Resin [K5] can be obtained by reacting substances.
  • the amount of (a) to be reacted with the copolymer is preferably 5 to 100 mol per 100 mol of (b). Since the cyclic ether has high reactivity and unreacted (b) does not easily remain, (b1) is preferable as (b) used in resin [K5], and (b1-1) is more preferable.
  • Resin [K6] is a resin obtained by reacting resin [K5] with a carboxylic acid anhydride.
  • the hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or carboxylic anhydride is reacted with the carboxylic anhydride.
  • Carboxylic anhydrides include succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, and 3,4,5,6-tetrahydrophthalic acid.
  • carboxylic acid anhydride is preferably 0.1 to 1 mol per 1 mol of (a).
  • Specific resins (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] Resin [K1] such as decyl acrylate/(meth)acrylic acid copolymer; 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate/benzyl (meth)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-epoxytricycl
  • Resin [K6] such as a resin obtained by further reacting a resin obtained by reacting acrylic acid with succinic anhydride.
  • resin (B) a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, a cyclic ether structure having 2 to 4 carbon atoms and ethylenically unsaturated A copolymer containing a structural unit having a bond (resin [K1] or resin [K2]) or resin [K6] is preferred.
  • the polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 500 to 100,000, more preferably 600 to 50,000, still more preferably 700 to 30,000.
  • the molecular weight is within the above range, the hardness of the color filter is improved, the residual film rate is high, the solubility of the unexposed portion in the developing solution is good, and the resolution of the colored pattern tends to be improved.
  • the dispersion degree [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1-6, more preferably 1.2-4.
  • the acid value of the resin (B) is preferably 10-170 mg-KOH/g, more preferably 20-150 mg-KOH/g, still more preferably 30-135 mg-KOH/g, in terms of solid content.
  • the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be determined, for example, by titration using an aqueous potassium hydroxide solution. .
  • the content of the resin (B) is preferably 7 to 80% by mass, more preferably 13 to 75% by mass, still more preferably 17 to 70% by mass, and even more preferably, relative to the total solid content. is 17 to 55% by mass.
  • the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the residual film rate tend to be improved.
  • the polymerizable compound (C) is a compound that can be polymerized by an active radical and/or an acid generated from the polymerization initiator (D). is a (meth)acrylic acid ester compound.
  • the polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds.
  • examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa( meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl ) isocyanurate, ethylene oxide-modified pent
  • At least one selected from the group consisting of trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and ethylene oxide-modified dipentaerythritol hexa(meth)acrylate is preferred.
  • the weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 or more and 1,500 or less.
  • the content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 10 to 60% by mass, still more preferably 12 to 55% by mass, based on the total solid content. be.
  • the content of the polymerizable compound (C) is within the above range, there is a tendency that the residual film ratio at the time of forming the colored pattern and the chemical resistance of the color filter are improved.
  • the polymerization initiator (D) is a compound capable of initiating polymerization by generating active radicals, acids, etc. by the action of light or heat.
  • the colored curable composition of the present invention contains an oxime compound as a polymerization initiator (D).
  • the oxime compound is preferably an O-acyl oxime compound having a partial structure represented by formula (d1). Below, * represents a bond.
  • Examples of the oxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1- On-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]ethan-1-imine, N-acetoxy-1-[9-ethyl-6- ⁇ 2-methyl-4-(3,3-dimethyl-2,4-di Oxacyclopentanylmethyloxy)benzoyl ⁇ -9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)
  • Irgacure OXE01, OXE02, OXE03 (manufactured by BASF), N-1919 (manufactured by ADEKA), PBG-314, PBG-317, PBG-326, PBG-327, PBG-329 (manufactured by Changzhou Power Electronics New Materials Co., Ltd.) ) may be used.
  • oxime compounds include N-acetyloxy-1-[4-(2-hydroxyethyloxy)phenylsulfanylphenyl]propan-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfanylphenyl )-3-cyclohexylpropan-1-one-2-imine, 2-[(acetyloxy)imino]-3-cyclohexyl-1-[4-(phenylsulfanyl)phenyl]propan-1-one, N-benzoyloxy -1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine and N-benzoyloxy-1 -(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine is
  • the colored curable composition of the present invention may contain a polymerization initiator other than the oxime compound as the polymerization initiator (D).
  • a polymerization initiator other than the oxime compound as the polymerization initiator (D).
  • examples of other polymerization initiators include alkylphenone compounds and triazines.
  • polymerization initiators that generate active radicals such as compounds, acylphosphine oxide compounds and biimidazole compounds.
  • the alkylphenone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3).
  • the benzene ring may have a substituent.
  • Examples of compounds having a partial structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4 -morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one etc.
  • Commercially available products such as Irgacure 369, 907 and 379 (manufactured by BASF) may also be used.
  • Examples of compounds having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2 -hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, ⁇ , ⁇ -diethoxy Acetophenone, benzyl dimethyl ketal and the like can be mentioned.
  • the alkylphenone compound is preferably a compound having a partial structure represented by formula (d2).
  • triazine compound 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-methoxy styryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4 -bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,
  • acylphosphine oxide compound examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
  • Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may also be used.
  • biimidazole compound examples include 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(alkoxyphenyl)biimidazole, 2,2′-bis (2-chlorophenyl)-4,4′,5,5′-tetra(dialkoxyphenyl)biimidazole, 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetra(triphen
  • Further polymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4; Benzophenone compounds such as '-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2 -quinone compounds such as ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like. These are preferably used in combination with a polymerization initiation aid (D1) (particularly
  • polymerization initiators include, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl Onium salts such as methylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylates , acid-generating polymerization initiators such as benzoin tosylate.
  • the content of the oxime compound in the polymerization initiator (D) is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably It is 98% by mass or more, and may be 100% by mass.
  • the content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). part by mass.
  • 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 color filter.
  • the polymerization initiation aid (D1) is a compound or a sensitizer used to accelerate the polymerization of the polymerizable compound whose polymerization has been initiated by the polymerization initiator. When the polymerization initiation aid (D1) is included, it is usually used in combination with the polymerization initiator (D). Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds and carboxylic acid compounds.
  • amine compound examples include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 -2-ethylhexyl dimethylaminobenzoate, N,N-dimethyl p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis (Ethylmethylamino)benzophenone and the like can be mentioned, and 4,4′-bis(diethylamino)benzophenone is particularly preferable.
  • EAB-F manufactured by Hodogaya Chemical Industry Co., Ltd.
  • alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-di butoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene and the like.
  • thioxanthone compounds examples 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, naphthoxyacetic acid and the like.
  • the content is preferably 0.1 to 30 parts by mass, with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is preferably 1 to 20 parts by mass.
  • the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of color filters tends to improve.
  • the carbonate compound (E) is a compound in which one or two of the two hydrogen atoms of carbonic acid are substituted with an optionally substituted hydrocarbon group.
  • the carbonate compound (E) is preferably a compound represented by formula (I).
  • R 1 and R 2 each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. ]
  • the number of carbon atoms in the hydrocarbon group represented by R 1 and R 2 is preferably 4-20, more preferably 4-15, still more preferably 4-10.
  • Hydrocarbon groups having 1 to 20 carbon atoms represented by R 1 and R 2 include R a1 to R a14 , R b1 to R b3 , R x2 , R x4 , R x5 , R x11 to R x13 , R x15 to R x17 , R y1 to R y5 , R y11 to R y13 and R y15 to R y17 include the groups exemplified as the hydrocarbon groups, straight-chain alkyl groups, branched-chain alkyl groups and the like.
  • saturated aliphatic hydrocarbon groups alkenyl groups, unsaturated aliphatic hydrocarbon groups such as alkynyl groups, saturated alicyclic hydrocarbon groups such as cycloalkyl groups, unsaturated alicyclic hydrocarbon groups such as cycloalkenyl groups, and aliphatic hydrocarbon groups such as saturated or unsaturated polycyclic hydrocarbon groups; aromatic hydrocarbon groups; It may be any of a combination of groups and the like.
  • the hydrocarbon group having 1 to 20 carbon atoms represented by R 1 and R 2 may have a substituent, and the substituent may be a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. , nitro group, cyano group, —OR xa1 , —CO 2 R xa1 , —SR xa1 , —SO 2 R xa1 , —SO 3 R xa1 , —SO 2 NR xa1 R xa2 and —NR xa1 R xa2 and the like. (provided that R xa1 and R xa2 are the same as above).
  • At least one of R 1 and R 2 is an optionally substituted linear or branched C 1-20 alkyl group, or an optionally substituted C 6 It is preferably an aromatic hydrocarbon group of up to 20 (hereinafter, the aromatic hydrocarbon group may be referred to as an aryl group) or an optionally substituted aralkyl group of 7 to 20 carbon atoms. Both R 1 and R 2 may independently have a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent or a substituent. It is more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms which may have a substituent.
  • the linear or branched alkyl group having 1 to 20 carbon atoms representing R 1 and R 2 is more preferably a linear or branched alkyl group having 4 to 20 carbon atoms.
  • a secondary or tertiary alkyl group having 4 to 20 carbon atoms is more preferred, and a tertiary alkyl group having 4 to 20 carbon atoms is particularly preferred.
  • R 1 and R 2 is an optionally substituted tertiary alkyl group having 4 to 20 carbon atoms and an optionally substituted aryl group having 6 to 20 carbon atoms. , or an optionally substituted aralkyl group having 7 to 20 carbon atoms, and both R 1 and R 2 each independently have an optionally substituted carbon number It is a 4-20 tertiary alkyl group, an optionally substituted C6-20 aryl group, or an optionally substituted C7-20 aralkyl group. more preferred.
  • the tertiary alkyl group is preferably a t-butyl group
  • the aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 10 carbon atoms
  • phenyl and the aralkyl group having 7 to 20 carbon atoms is preferably an aralkyl group having 7 to 10 carbon atoms, more preferably a benzyl group.
  • the content of the carbonate compound (E) is, for example, 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and for example 20% by mass or less, preferably It is 15% by mass or less, more preferably 10% by mass or less.
  • the amount of the carbonate compound (E) is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, preferably 40 parts by mass or less, and 25 parts by mass or less, relative to 100 parts by mass of the phthalocyanine compound. more preferred.
  • the amount of the carbonate compound (E) is, for example, 25 parts by mass or more, preferably 100 parts by mass or more, more preferably 150 parts by mass or more, and still more preferably 180 parts by mass or more with respect to 100 parts by mass of the aluminum phthalocyanine compound. Also, for example, it is 350 parts by mass or less, preferably 300 parts by mass or less, more preferably 250 parts by mass or less. Furthermore, the content ratio of the carbonate compound (E) to the polymerization initiator (D) (carbonate compound (E)/polymerization initiator (D)) is, for example, 0.1 or more, preferably 0.2 or more, more preferably 0 0.5 or more and, for example, 10 or less, preferably 8 or less, more preferably 5 or less. When the content of the carbonate compound (E) is within the above range, it is possible to provide a colored curable composition with better pattern stability even after storage.
  • Leveling agent (F) examples include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymerizable group in the side chain.
  • silicone-based surfactants include surfactants having a siloxane bond in the molecule.
  • Toray Silicone DC3PA, Toray SH7PA, Toray DC11PA, Toray SH21PA, Toray SH28PA, Toray SH29PA, Toray SH30PA, Toray SH8400 (trade name: Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, 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), etc. .
  • fluorine-based surfactants examples include surfactants having a fluorocarbon chain in the molecule.
  • silicone-based surfactants having fluorine atoms include surfactants having siloxane bonds and fluorocarbon chains in the molecule.
  • Megafac registered trademark
  • Megafac BL20 Megafac F475, F477 and F443 (manufactured by DIC Corporation) and the like can be mentioned.
  • the content of the leveling agent (F) is preferably 0.001 to 0.2% by mass, more preferably 0.002 to 0.1% by mass, and still more preferably, relative to the total amount of the colored curable composition. is 0.005 to 0.05% by mass. 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 color filter can be improved.
  • the solvent (G) is not particularly limited, and solvents commonly used in the field can be used.
  • solvents commonly used in the field can be used.
  • ester solvent solvent containing -COO- in the molecule but not containing -O-
  • ether solvent solvent containing -O- in the molecule but not containing -COO-
  • ether ester solvent solvent containing -COO- in the molecule solvent containing -COO- and -O-
  • ketone solvent solvent containing -CO- in the molecule and not containing -COO-
  • alcohol solvent containing OH in the molecule, -O-, - solvents containing no CO- and -COO-
  • aromatic hydrocarbon solvents amide solvents, dimethyl sulfoxide and the like.
  • 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 ⁇ -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, and 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, phenetol and methylanisole and the like.
  • Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether a
  • Ketone solvents include 4-hydroxy-4-methyl-2-pentanone (sometimes referred to as diacetone alcohol), acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone, isophorone, and the like.
  • Alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.
  • Aromatic hydrocarbon solvents include benzene, toluene, xylene and mesitylene.
  • Amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.
  • Solvent (G) is preferably one or more selected from the group consisting of ether solvents, ether ester solvents and amide solvents, more preferably includes ether solvents, ether ester solvents and amide solvents, diethylene glycol methyl ethyl More preferred are ethers, propylene glycol monomethyl ether acetate, and N-methylpyrrolidone. Moreover, the solvent (G) preferably contains one or more selected from the group consisting of ether ester solvents and ketone solvents.
  • organic solvents having a boiling point of 120° C. or higher and 180° C. or lower at 1 atm are preferable from the viewpoint of coating properties and drying properties.
  • Such solvents include propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl- It is preferably at least one selected from the group consisting of 2-pentanone and N,N-dimethylformamide, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, and 4- More preferably, it is at least one selected from the group consisting of hydroxy-4-methyl-2-pentanone.
  • the content of the solvent (G) is preferably 70-95% by mass, more preferably 75-92% by mass, relative to the total amount of the colored curable composition.
  • the solids content of the colored curable composition is preferably 5-30% by weight, more preferably 8-25% by weight.
  • the colored curable composition may optionally contain additives known in the art such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc. .
  • the colored curable composition includes, for example, a coloring agent (A) containing a phthalocyanine compound, a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a carbonate compound (E), and if necessary It can be prepared by mixing the polymerization initiation aid (D1), leveling agent (F), solvent (G) and other components used.
  • the phthalocyanine compound may be included in the dispersion in advance.
  • the pigment may also be included in the dispersion in advance.
  • the phthalocyanine compound and the pigment may be prepared as one dispersion or as separate dispersions.
  • the desired colored curable composition can be prepared by mixing the remaining components with the dispersion liquid so as to have a predetermined concentration.
  • the dye may be dissolved in part or all of the solvent (G) in advance to prepare a solution. It is preferable to filter the solution through a filter having a pore size of about 0.01 to 1 ⁇ m. It is preferable to filter the colored curable composition after mixing through a filter having a pore size of about 0.01 to 10 ⁇ m.
  • Examples of the method for producing a colored pattern of a color filter from the colored curable composition of the present invention include a photolithography method, an inkjet method, a printing method and the like. Among them, the photolithographic method is preferred. Photolithography is a method in which the colored curable composition is applied to a substrate, dried to form a composition layer, exposed through a photomask, and developed. In the photolithographic method, a colored coating film, which is a cured product of the 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 color filter of the present invention.
  • the film thickness of the color filter (colored coating film) is, for example, 30 ⁇ m or less, preferably 20 ⁇ m or less, more preferably 6 ⁇ m or less, even more preferably 3 ⁇ m or less, even more preferably 1.5 ⁇ m or less, and particularly preferably 0.5 ⁇ m or less. , preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and still more preferably 0.3 ⁇ m or more.
  • the substrate examples include glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass whose surface is coated with silica; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; A thin film of aluminum, silver, silver/copper/palladium alloy, etc. is formed on the substrate. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates. Alternatively, a substrate obtained by subjecting a silicon substrate to HMDS processing may be used.
  • each color pixel by the photolithographic method can be carried out using a known or commonly used apparatus and conditions. For example, it can be produced as follows. First, a colored curable composition is applied onto a substrate, dried by heating (pre-baking) and/or dried under reduced pressure to remove volatile components such as solvents, and dried to obtain a smooth composition layer. Examples of coating methods include a spin coating method, a slit coating method, a slit and spin coating method, and the like.
  • the temperature for heat drying is preferably 30 to 120°C, more preferably 50 to 110°C.
  • the heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.
  • drying under reduced pressure it is preferably carried out at a pressure of 50 to 150 Pa and a temperature of 20 to 25°C.
  • the film thickness of the composition layer is not particularly limited, and may be appropriately selected according to the desired film thickness of the color filter.
  • the composition layer is then exposed through a photomask to form the desired colored pattern.
  • the pattern on the photomask is not particularly limited, and a pattern suitable for the intended use is used.
  • the light source used for exposure is preferably a light source that emits light with a wavelength of 250 to 450 nm. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges.
  • a reduction projection exposure apparatus such as a mask aligner and a stepper, or a proximity exposure apparatus. preferable.
  • a colored pattern is formed on the substrate by developing the exposed composition layer in contact with a developer.
  • a developer for example, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate and tetramethylammonium hydroxide are preferred.
  • the concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.
  • the developer may contain a surfactant.
  • the developing method may be any of a puddle method, a dipping method, a spray method, and the like.
  • the substrate may be tilted at any angle during development. It is preferable to wash with water after development.
  • the post-baking temperature is preferably 80 to 250°C, more preferably 100 to 245°C.
  • Post-baking time is preferably 1 to 120 minutes, more preferably 2 to 30 minutes.
  • the colored pattern and colored coating film thus obtained are useful as a color filter, and the color filter can be used for display devices (e.g., liquid crystal display devices, organic EL display devices, etc.), electronic paper, solid-state imaging devices, and the like. It is useful as a color filter used for display devices (e.g., liquid crystal display devices, organic EL display devices, etc.), electronic paper, solid-state imaging devices, and the like. It is useful as a color filter used for display devices (e.g., liquid crystal display devices, organic EL display devices, etc.), electronic paper, solid-state imaging devices, and the like. It is useful as a color filter used for
  • Resin (B-1) has the following structural units.
  • the mixture was further stirred at 120° C. for 30 minutes to carry out a copolymerization reaction to produce an addition copolymer. Thereafter, the inside of 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 introduced into the above addition copolymer solution.
  • the reaction was continued at 110° C. for 10 hours to cleave the epoxy group and introduce a polymerizable unsaturated bond into the side chain of the polymer at the same time as the reaction between the epoxy group derived from glycidyl methacrylate and acrylic acid.
  • Dispersion 1 (Preparation of Dispersion 1) C. I. Pigment Blue 15: 12.0 parts of 4, 3.6 parts of dispersant (BYKLPN-6919 manufactured by BYK), 5.4 parts of resin (B-1) (solid content conversion), propylene glycol monomethyl ether acetate 79 The parts were mixed and 300 parts of 0.4 mm zirconia beads were added and shaken for 1 hour using paint conditioner (manufactured by LAU). After that, the zirconia beads were removed by filtration to obtain Dispersion Liquid 1.
  • dispersion liquid 2 (Preparation of dispersion liquid 2) 5.0 parts of the compound (x1), 4.0 parts of the dispersant (BYKLPN-6919 manufactured by BYK), 4.0 parts of the resin (B-1) (in terms of solid content), 87 parts of propylene glycol monomethyl ether acetate was mixed, 300 parts of 0.4 mm zirconia beads were added and shaken for 1 hour using a paint conditioner (manufactured by LAU). After that, the zirconia beads were removed by filtration to obtain Dispersion Liquid 2.
  • a paint conditioner manufactured by LAU
  • dispersion liquid 4 (Preparation of dispersion liquid 4) 5.0 parts of the compound (x2), 4.0 parts of the dispersant (BYKLPN-6919 manufactured by BYK), 4.0 parts of the resin (B-1) (in terms of solid content), 87 parts of propylene glycol monomethyl ether acetate was mixed, 300 parts of 0.4 mm zirconia beads were added and shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to obtain Dispersion Liquid 4.
  • a paint conditioner manufactured by LAU
  • each component is as follows.
  • each of the colored curable compositions of Examples and Comparative Examples was applied by spin coating so that the film thickness after post-baking was 0.8 ⁇ m, and then pre-baked at 80° C. for 2 minutes. to obtain a colored composition layer.
  • the substrate on which the colored composition layer was formed was irradiated with light at an exposure amount of 300 mJ/cm 2 (365 nm standard) using an exposure machine (NSR-1755i7A; manufactured by Nikon Corporation). A photomask on which a 2.0 ⁇ m square dot pattern was formed was used.
  • the colored composition layer after light irradiation is immersed in an aqueous developer containing tetramethylammonium hydroxide for 30 seconds at 23 ° C. After washing, the substrate after development (before post-baking) is post-baked at 230 ° C. for 10 minutes. , to obtain a colored pattern I after post-baking. Further, after storing the colored curable compositions of Examples 1 and 2 and Comparative Example 1 at 40° C. for 3 days, post-baked colored patterns II were obtained in the same manner as described above. After storing the colored curable compositions of Examples 3 to 6 at 40° C. for one day, a post-baked colored pattern II was obtained in the same manner as described above.

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Abstract

The present invention addresses the problem of providing a colored curable composition in which the rate of change in the line width of a pattern obtained therefrom is small even when the colored curable composition is used after storage, in other words, the problem of providing a colored curable composition that offers suitable pattern stability even after storage.　A colored curable composition according to the present invention contains a coloring agent, a resin, a polymerizable compound, a polymerization initiator, and a carbonate compound. The coloring agent includes a phthalocyanine compound, and the polymerization initiator includes an oxime compound.

Description

着色硬化性組成物colored curable composition
　本発明は、着色硬化性組成物に関する。 The present invention relates to a colored curable composition.
　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、及びＣＣＤやＣＭＯＳセンサ等の固体撮像素子等に使用されるカラーフィルタは、着色硬化性組成物から製造される。着色硬化性組成物には種々の着色剤が含まれており、例えばフタロシアニン化合物を含む着色硬化性組成物が知られている（特許文献１、２）。 Color filters used in display devices such as liquid crystal display devices, electroluminescence display devices and plasma displays, and solid-state imaging devices such as CCD and CMOS sensors are manufactured from colored curable compositions. Colored curable compositions contain various colorants, and for example, colored curable compositions containing phthalocyanine compounds are known (Patent Documents 1 and 2).
特開２０１８－０９１９１６号公報JP 2018-091916 A 特開２０１６－０７５８３７号公報JP 2016-075837 A
　しかしながら、フタロシアニン化合物を含む着色硬化性組成物を一定期間保存した後にパターンを作製すると、保存することなくパターンを作製した場合と比較して、得られるパターンの線幅が小さくなったり、パターンが消失したりするという問題があった。そこで、本発明は、保存後の着色硬化性組成物を用いた場合であっても、得られるパターンの線幅変化率が小さい着色硬化性組成物を提供すること、すなわち保存後であってもパターン安定性が良好な着色硬化性組成物を提供することを課題とする。 However, when a pattern is produced after storing a colored curable composition containing a phthalocyanine compound for a certain period of time, the line width of the resulting pattern becomes smaller, or the pattern disappears, compared to the case where the pattern is produced without being stored. There was a problem that Therefore, the present invention provides a colored curable composition in which the line width change rate of the pattern obtained is small even when the colored curable composition after storage is used, that is, even after storage An object of the present invention is to provide a colored curable composition with good pattern stability.
　本発明は、以下の発明を含む。
［１］　着色剤、樹脂、重合性化合物、重合開始剤、及びカルボナート化合物を含有し、
　前記着色剤が、フタロシアニン化合物を含み、
　前記重合開始剤が、オキシム化合物を含む着色硬化性組成物。
［２］　前記カルボナート化合物が、式（Ｉ）で表される化合物である［１］に記載の着色硬化性組成物。 The present invention includes the following inventions.
[1] containing a coloring agent, a resin, a polymerizable compound, a polymerization initiator, and a carbonate compound,
the coloring agent comprises a phthalocyanine compound,
The colored curable composition, wherein the polymerization initiator contains an oxime compound.
[2] The colored curable composition according to [1], wherein the carbonate compound is a compound represented by formula (I).
Figure JPOXMLDOC01-appb-C000010
 ［式（Ｉ）中、Ｒ1及びＲ2は、それぞれ独立して、置換基を有していてもよい炭素数１～２０の炭化水素基を表す。］
［３］　前記Ｒ1及びＲ2の少なくとも一方が、置換基を有していてもよい炭素数４～２０の第三級アルキル基、置換基を有していてもよい炭素数６～２０のアリール基、又は置換基を有していてもよい炭素数７～２０のアラルキル基である［２］に記載の着色硬化性組成物。
［４］　前記フタロシアニン化合物が、式（Ｘ１）～式（Ｘ３）で表される化合物のいずれかである［１］～［３］のいずれかに記載の着色硬化性組成物。
Figure JPOXMLDOC01-appb-C000010
 [In formula (I), R 1 and R 2 each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. ]
[3] At least one of R 1 and R 2 is an optionally substituted tertiary alkyl group having 4 to 20 carbon atoms, or an optionally substituted C 6 to 20 The colored curable composition according to [2], which is an aryl group or an optionally substituted aralkyl group having 7 to 20 carbon atoms.
[4] The colored curable composition according to any one of [1] to [3], wherein the phthalocyanine compound is any one of compounds represented by formulas (X1) to (X3).
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
 ［式（Ｘ１）中、
　Ｘx1～Ｘx4は、それぞれ独立に、－Ｒx4、－ＯＲx4、－ＳＲx4、－ＳＯ3Ｈ、－ＳＯ3 -Ｔ+、－ＳＯ3ＲX10、－ＳＯ2ＮＲX11ＲX12、ハロゲン原子、又はニトロ基を表す。
　Ｒx4は、置換基を有していてもよい炭素数１～２０の炭化水素基を表し、該炭化水素基の炭素数が２～２０であり且つ該炭化水素基が－ＣＨ2－を有する場合、該－ＣＨ2－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わっていてもよい。
　Ｔ+は、+Ｎ（ＲX13）4又はアルカリ金属イオンを表し、ＲX13は、それぞれ独立に、水素原子又は炭素数１～２０の炭化水素基を表す。
　ＲX10は、炭素数１～２０の飽和炭化水素基を表す。
　ＲX11及びＲX12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１～２０の炭化水素基を表す。
　ｎｘ１～ｎｘ４は、それぞれ独立に、０～４の整数を表す。
式（Ｘ２）中、
　Ｍ1は、金属原子、金属酸化物、金属水酸化物、金属ハロゲン化物、リン含有基結合金属、ケイ素含有基結合金属、オキシカルボニル含有基結合金属、またはオキシスルホニル含有基結合金属を表す。
　Ｘx1～Ｘx4及びｎｘ１～ｎｘ４は、前記に同じ。
式（Ｘ３）中、
　Ｍ2及びＭ3は、それぞれ独立に、金属原子、金属酸化物、金属水酸化物、または金属ハロゲン化物を表す。
　Ｌは、－Ｏ－ＳｉＲa6Ｒa7－Ｏ－、－Ｏ－ＳｉＲa8Ｒa9－Ｏ－ＳｉＲa10Ｒa11－Ｏ－、または－Ｏ－Ｐ（＝Ｏ）Ｒa12－Ｏ－を表す。
　Ｒa6～Ｒa12は、それぞれ独立に、水素原子、ヒドロキシ基、置換基を有していてもよい炭素数１～２０の炭化水素基、又は置換基を有していてもよい炭素数１～２０の複素環基を表し、Ｒa6とＲa7、Ｒa8とＲa9、またはＲa10とＲa11は、互いに結合して環を形成してもよい。該炭化水素基の炭素数が２～２０であり且つ該炭化水素基が－ＣＨ2－を有する場合、該－ＣＨ2－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わっていてもよい。
　Ｘx5～Ｘx12は、それぞれ独立に、－Ｒx5、－ＯＲx5、－ＳＲx5、－ＳＯ3Ｈ、－ＳＯ3 -Ｑ+、－ＳＯ3ＲX14、－ＳＯ2ＮＲX15ＲX16、ハロゲン原子、又はニトロ基を表す。
　Ｒx5は、置換基を有していてもよい炭素数１～２０の炭化水素基を表し、該炭化水素基の炭素数が２～２０であり且つ該炭化水素基が－ＣＨ2－を有する場合、該－ＣＨ2－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わっていてもよい。
　Ｑ+は、+Ｎ（ＲX17）4又はアルカリ金属イオンを表し、ＲX17は、それぞれ独立に、水素原子又は炭素数１～２０の炭化水素基を表す。
　ＲX14は、炭素数１～２０の飽和炭化水素基を表す。
　ＲX15及びＲX16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１～２０の炭化水素基を表す。
　ｎｘ５～ｎｘ１２は、それぞれ独立に、０～４の整数を表す。］
［５］　前記フタロシアニン化合物が、式（Ｘａ）又は式（Ｘｂ）で表される化合物である［１］～［４］のいずれかに記載の着色硬化性組成物。
Figure JPOXMLDOC01-appb-C000013
 [In the formula (X1),
X x1 to X x4 each independently represent -R x4 , -OR x4 , -SR x4 , -SO 3 H, -SO 3 - T + , -SO 3 R x10 , -SO 2 NR x11 R x12 , halogen represents an atom or a nitro group.
R x4 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group having 2 to 20 carbon atoms and having —CH 2 — In some cases, the --CH 2 -- may be replaced with --O--, --S-- or --CO--.
T + represents + N(R X13 ) 4 or an alkali metal ion, and each R X13 independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
R X10 represents a saturated hydrocarbon group having 1 to 20 carbon atoms.
R X11 and R X12 each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
nx1 to nx4 each independently represent an integer of 0 to 4;
In formula (X2),
M 1 represents a metal atom, a metal oxide, a metal hydroxide, a metal halide, a phosphorus-containing group-bonded metal, a silicon-containing group-bonded metal, an oxycarbonyl-containing group-bonded metal, or an oxysulfonyl-containing group-bonded metal.
X x1 to X x4 and nx1 to nx4 are the same as above.
In formula (X3),
M 2 and M 3 each independently represent a metal atom, metal oxide, metal hydroxide, or metal halide.
L represents -O-SiR a6 R a7 -O-, -O-SiR a8 R a9 -O-SiR a10 R a11 -O-, or -OP(=O)R a12 -O-.
R a6 to R a12 each independently represent a hydrogen atom, a hydroxy group, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted C 1 to represents 20 heterocyclic groups, and R a6 and R a7 , R a8 and R a9 , or R a10 and R a11 may combine with each other to form a ring; When the hydrocarbon group has 2 to 20 carbon atoms and has —CH 2 —, the —CH 2 — may be replaced with —O—, —S— or —CO—. good.
X x5 to X x12 each independently represent -R x5 , -OR x5 , -SR x5 , -SO 3 H, -SO 3 - Q + , -SO 3 R x14 , -SO 2 NR x15 R x16 , halogen represents an atom or a nitro group.
R x5 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group having 2 to 20 carbon atoms, and the hydrocarbon group having —CH 2 — In some cases, the --CH 2 -- may be replaced with --O--, --S-- or --CO--.
Q + represents + N(R X17 ) 4 or an alkali metal ion, and each R X17 independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
R X14 represents a saturated hydrocarbon group having 1 to 20 carbon atoms.
R X15 and R X16 each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
nx5 to nx12 each independently represent an integer of 0 to 4; ]
[5] The colored curable composition according to any one of [1] to [4], wherein the phthalocyanine compound is a compound represented by Formula (Xa) or Formula (Xb).
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
 ［式（Ｘａ）中、
　Ｚは、ヒドロキシ基、塩素原子、－ＯＰ（＝Ｏ）Ｒa1Ｒa2、－Ｏ－ＳｉＲa3Ｒa4Ｒa5、－ＯＣ（＝Ｏ）Ｒa13、又は－ＯＳ（＝Ｏ）2Ｒa14を表す。
　Ｒa1～Ｒa5、及びＲa13～Ｒa14は、それぞれ独立に、水素原子、ヒドロキシ基、置換基を有していてもよい炭素数１～２０の炭化水素基、又は置換基を有していてもよい炭素数１～２０の複素環基を表し、Ｒa1とＲa2、またはＲa3～Ｒa5のいずれか二つは、互いに結合して環を形成してもよい。該炭化水素基の炭素数が２～２０であり且つ該炭化水素基が－ＣＨ2－を有する場合、該－ＣＨ2－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わっていてもよい。
　Ｘx1～Ｘx4及びｎｘ１～ｎｘ４は、前記に同じ。
式（Ｘｂ）中、
　Ｌ、Ｘx5～Ｘx12及びｎｘ５～ｎｘ１２は、前記に同じ。］
［６］　前記式（Ｘａ）で表される化合物が式（Ｘ０）又は式（ＸＩ）で表される化合物であり、式（Ｘｂ）で表される化合物が式（ＸＩＩ）で表される化合物である［５］に記載の着色硬化性組成物。
Figure JPOXMLDOC01-appb-C000015
 [in the formula (Xa),
Z is a hydroxy group, a chlorine atom, -OP(=O)R a1 R a2 , -O-SiR a3 R a4 R a5 , -OC(=O) R a13 or -OS(=O) 2 R a14 show.
R a1 to R a5 and R a13 to R a14 each independently have a hydrogen atom, a hydroxy group, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. any two of R a1 and R a2 or R a3 to R a5 may combine with each other to form a ring. When the hydrocarbon group has 2 to 20 carbon atoms and has —CH 2 —, the —CH 2 — may be replaced with —O—, —S— or —CO—. good.
X x1 to X x4 and nx1 to nx4 are the same as above.
In formula (Xb),
L, X x5 to X x12 and nx5 to nx12 are the same as above. ]
[6] The compound represented by formula (Xa) is a compound represented by formula (X0) or formula (XI), and the compound represented by formula (Xb) is a compound represented by formula (XII) The colored curable composition according to [5].
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
 ［式（ＸＩ）中、
　Ｒx1は、置換基を有していてもよい炭素数２～２０の脂肪族不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の芳香族炭化水素基を表し、Ｒx2は、水素原子、置換基を有していてもよい炭素数１～２０の炭化水素基、又はＺx2とＲx1とを結ぶ単結合を表す。
　Ｚx1及びＺx2は、それぞれ独立に、単結合又は酸素原子を表す。
式（Ｘ０）及び式（ＸＩ）中、
　Ｘx1～Ｘx4、ｎｘ１～ｎｘ４は、前記に同じ。
式（ＸＩＩ）中、
　Ｒx3は、置換基を有していてもよい炭素数２～２０の脂肪族不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の芳香族炭化水素基を表す。
　Ｚx3は、単結合又は酸素原子を表す。
　Ｘx5～Ｘx12、ｎｘ５～ｎｘ１２は、前記に同じ。］
［７］　［１］～［６］のいずれかに記載の着色硬化性組成物から形成されるカラーフィルタ。
［８］　［７］に記載のカラーフィルタを含む表示装置。
［９］　［７］に記載のカラーフィルタを含む固体撮像素子。
Figure JPOXMLDOC01-appb-C000018
 [in the formula (XI),
R x1 represents an optionally substituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, R x2 represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or a single bond connecting Z x2 and R x1 .
Z x1 and Z x2 each independently represent a single bond or an oxygen atom.
In formula (X0) and formula (XI),
X x1 to X x4 and nx1 to nx4 are the same as above.
In formula (XII),
R x3 represents an optionally substituted C 2-20 aliphatic unsaturated hydrocarbon group or an optionally substituted C 6-20 aromatic hydrocarbon group.
Z x3 represents a single bond or an oxygen atom.
X x5 to X x12 and nx5 to nx12 are the same as above. ]
[7] A color filter formed from the colored curable composition according to any one of [1] to [6].
[8] A display device including the color filter of [7].
[9] A solid-state imaging device including the color filter according to [7].
　本発明によれば、保存後の着色硬化性組成物を用いた場合であっても、得られるパターンの線幅変化率が小さい着色硬化性組成物を提供すること、すなわち保存後であってもパターン安定性が良好な着色硬化性組成物を提供することができる。 According to the present invention, even when the colored curable composition after storage is used, to provide a colored curable composition in which the line width change rate of the resulting pattern is small, that is, even after storage A colored curable composition with good pattern stability can be provided.
＜＜着色硬化性組成物＞＞
　本発明は、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）、及びカルボナート化合物（以下、カルボナート化合物（Ｅ）という場合がある）を含有し、前記着色剤（Ａ）が、フタロシアニン化合物を含み、前記重合開始剤（Ｄ）が、オキシム化合物を含む着色硬化性組成物を包含する。
　本発明の着色硬化性組成物は、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。
　本発明の着色硬化性組成物は、溶剤（以下、溶剤（Ｇ）という場合がある）を含んでいてもよい。
　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合せて使用することができる。 <<Colored curable composition>>
The present invention includes a coloring agent (hereinafter sometimes referred to as a coloring agent (A)), a resin (hereinafter sometimes referred to as a resin (B)), a polymerizable compound (hereinafter sometimes referred to as a polymerizable compound (C) ), a polymerization initiator (hereinafter sometimes referred to as a polymerization initiator (D)), and a carbonate compound (hereinafter sometimes referred to as a carbonate compound (E)), and the coloring agent (A) is a phthalocyanine compound and wherein the polymerization initiator (D) includes a colored curable composition containing an oxime compound.
The colored curable composition of the present invention may contain a leveling agent (hereinafter sometimes referred to as leveling agent (F)).
The colored curable composition of the present invention may contain a solvent (hereinafter sometimes referred to as solvent (G)).
In this specification, the compounds exemplified as each component can be used singly or in combination unless otherwise specified.
＜着色剤（Ａ）＞
　本発明に係る着色硬化性組成物は、着色剤としてフタロシアニン化合物を含む。前記フタロシアニン化合物としては、具体的には、下記式（Ｘ１）～式（Ｘ３）で表される化合物が挙げられる。以下、式（Ｘ１）～式（Ｘ３）で表される化合物の部分構造を挙げて本発明をより具体的に説明する。なお式（Ｘａ）、式（Ｘｂ）、式（Ｘ０）、式（ＸＩ）、式（ＸＩＩ）、式（ＹＩ）又は式（ＹＩＩ）と共通する定義は後述する。 <Colorant (A)>
The colored curable composition according to the present invention contains a phthalocyanine compound as a coloring agent. Specific examples of the phthalocyanine compound include compounds represented by the following formulas (X1) to (X3). Hereinafter, the present invention will be described more specifically with partial structures of the compounds represented by formulas (X1) to (X3). Definitions common to Formula (Xa), Formula (Xb), Formula (X0), Formula (XI), Formula (XII), Formula (YI) or Formula (YII) will be described later.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
 ［式（Ｘ１）中、
　Ｘx1～Ｘx4は、それぞれ独立に、－Ｒx4、－ＯＲx4、－ＳＲx4、－ＳＯ3Ｈ、－ＳＯ3 -Ｔ+、－ＳＯ3ＲX10、－ＳＯ2ＮＲX11ＲX12、ハロゲン原子、又はニトロ基を表す。
　Ｒx4は、置換基を有していてもよい炭素数１～２０の炭化水素基を表し、該炭化水素基の炭素数が２～２０であり且つ該炭化水素基が－ＣＨ2－を有する場合、該－ＣＨ2－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わっていてもよい。
　Ｔ+は、+Ｎ（ＲX13）4又はアルカリ金属イオンを表し、ＲX13は、それぞれ独立に、水素原子又は炭素数１～２０の炭化水素基を表す。
　ＲX10は、炭素数１～２０の飽和炭化水素基を表す。
　ＲX11及びＲX12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１～２０の炭化水素基を表す。
　ｎｘ１～ｎｘ４は、それぞれ独立に、０～４の整数を表す。
式（Ｘ２）中、
　Ｍ1は、金属原子、金属酸化物、金属水酸化物、金属ハロゲン化物、リン含有基結合金属、ケイ素含有基結合金属、オキシカルボニル含有基結合金属、またはオキシスルホニル含有基結合金属を表す。
　Ｘx1～Ｘx4及びｎｘ１～ｎｘ４は、前記に同じ。
式（Ｘ３）中、
　Ｍ2及びＭ3は、それぞれ独立に、金属原子、金属酸化物、金属水酸化物、または金属ハロゲン化物を表す。
　Ｌは、－Ｏ－ＳｉＲa6Ｒa7－Ｏ－、－Ｏ－ＳｉＲa8Ｒa9－Ｏ－ＳｉＲa10Ｒa11－Ｏ－、または－Ｏ－Ｐ（＝Ｏ）Ｒa12－Ｏ－を表す。
　Ｒa6～Ｒa12は、それぞれ独立に、水素原子、ヒドロキシ基、置換基を有していてもよい炭素数１～２０の炭化水素基、又は置換基を有していてもよい炭素数１～２０の複素環基を表し、Ｒa6とＲa7、Ｒa8とＲa9、またはＲa10とＲa11は、互いに結合して環を形成してもよい。該炭化水素基の炭素数が２～２０であり且つ該炭化水素基が－ＣＨ2－を有する場合、該－ＣＨ2－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わっていてもよい。
　Ｘx5～Ｘx12は、それぞれ独立に、－Ｒx5、－ＯＲx5、－ＳＲx5、－ＳＯ3Ｈ、－ＳＯ3 -Ｑ+、－ＳＯ3ＲX14、－ＳＯ2ＮＲX15ＲX16、ハロゲン原子、又はニトロ基を表す。
　Ｒx5は、置換基を有していてもよい炭素数１～２０の炭化水素基を表し、該炭化水素基の炭素数が２～２０であり且つ該炭化水素基が－ＣＨ2－を有する場合、該－ＣＨ2－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わっていてもよい。
　Ｑ+は、+Ｎ（ＲX17）4又はアルカリ金属イオンを表し、ＲX17は、それぞれ独立に、水素原子又は炭素数１～２０の炭化水素基を表す。
　ＲX14は、炭素数１～２０の飽和炭化水素基を表す。
　ＲX15及びＲX16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１～２０の炭化水素基を表す。
　ｎｘ５～ｎｘ１２は、それぞれ独立に、０～４の整数を表す。］
Figure JPOXMLDOC01-appb-C000021
 [In the formula (X1),
X x1 to X x4 each independently represent -R x4 , -OR x4 , -SR x4 , -SO 3 H, -SO 3 - T + , -SO 3 R x10 , -SO 2 NR x11 R x12 , halogen represents an atom or a nitro group.
R x4 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group having 2 to 20 carbon atoms and having —CH 2 — In some cases, the --CH 2 -- may be replaced with --O--, --S-- or --CO--.
T + represents + N(R X13 ) 4 or an alkali metal ion, and each R X13 independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
R X10 represents a saturated hydrocarbon group having 1 to 20 carbon atoms.
R X11 and R X12 each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
nx1 to nx4 each independently represent an integer of 0 to 4;
In formula (X2),
M 1 represents a metal atom, a metal oxide, a metal hydroxide, a metal halide, a phosphorus-containing group-bonded metal, a silicon-containing group-bonded metal, an oxycarbonyl-containing group-bonded metal, or an oxysulfonyl-containing group-bonded metal.
X x1 to X x4 and nx1 to nx4 are the same as above.
In formula (X3),
M 2 and M 3 each independently represent a metal atom, metal oxide, metal hydroxide, or metal halide.
L represents -O-SiR a6 R a7 -O-, -O-SiR a8 R a9 -O-SiR a10 R a11 -O-, or -OP(=O)R a12 -O-.
R a6 to R a12 each independently represent a hydrogen atom, a hydroxy group, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted C 1 to represents 20 heterocyclic groups, and R a6 and R a7 , R a8 and R a9 , or R a10 and R a11 may combine with each other to form a ring; When the hydrocarbon group has 2 to 20 carbon atoms and has —CH 2 —, the —CH 2 — may be replaced with —O—, —S— or —CO—. good.
X x5 to X x12 each independently represent -R x5 , -OR x5 , -SR x5 , -SO 3 H, -SO 3 - Q + , -SO 3 R x14 , -SO 2 NR x15 R x16 , halogen represents an atom or a nitro group.
R x5 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group having 2 to 20 carbon atoms, and the hydrocarbon group having —CH 2 — In some cases, the --CH 2 -- may be replaced with --O--, --S-- or --CO--.
Q + represents + N(R X17 ) 4 or an alkali metal ion, and each R X17 independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
R X14 represents a saturated hydrocarbon group having 1 to 20 carbon atoms.
R X15 and R X16 each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
nx5 to nx12 each independently represent an integer of 0 to 4; ]
　Ｍ1～Ｍ3で表される金属原子としては、具体的に、Ｌｉ、Ｎａ、Ｋ、Ｍｇ、Ｔｉ、Ｚｒ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ、Ｒｈ、Ｐｄ、Ｏｓ、Ｉｒ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎ、Ｃｄ、Ｈｇ、Ａｌ、Ｇａ、Ｉｎ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂ、Ｓｂ、及びＢｉ等が挙げられる。なかでも特に、Ｃｕ、Ｎｉ、Ｚｎ、又はＡｌが好ましい。 Specific metal atoms represented by M 1 to M 3 include Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, and the like. Among them, Cu, Ni, Zn, or Al is particularly preferable.
　Ｍ1～Ｍ3で表される金属酸化物としては、具体的に、ＶＯ、ＧｅＯ等が好ましく挙げられる。 As metal oxides represented by M 1 to M 3 , specifically, VO, GeO and the like are preferably mentioned.
　Ｍ1～Ｍ3で表される金属水酸化物としては、具体的に、ＡｌＯＨ、Ｓｉ（ＯＨ）2、Ｃｒ（ＯＨ）2、Ｓｎ（ＯＨ）2等が好ましく挙げられる。 Specific preferred metal hydroxides represented by M 1 to M 3 include AlOH, Si(OH) 2 , Cr(OH) 2 and Sn(OH) 2 .
　Ｍ1～Ｍ3で表される金属ハロゲン化物としては、ＡｌＣｌ、ＳｉＣｌ2、ＶＣｌ、ＶＣｌ2、ＶＯＣｌ、ＦｅＣｌ、ＧａＣｌ、ＺｒＣｌ等が挙げられる。 Examples of metal halides represented by M 1 to M 3 include AlCl, SiCl 2 , VCl, VCl 2 , VOCl, FeCl, GaCl and ZrCl.
　Ｍ1で表されるリン含有基結合金属は、リン原子を含有する基が金属原子に結合した構造を有しており、リン含有基が結合する金属原子としては、前述のＭ1～Ｍ3で表される金属原子として説明したものが挙げられる。リン含有基としては、具体的に、－ＯＰ（＝Ｏ）Ｒa1Ｒa2で表される基が好ましい。 The phosphorus-containing group-bonded metal represented by M 1 has a structure in which a group containing a phosphorus atom is bonded to a metal atom . Examples of the metal atom represented by are those described above. Specifically, the phosphorus-containing group is preferably a group represented by -OP(=O)R a1 R a2 .
　Ｍ1で表されるケイ素含有基結合金属は、ケイ素原子を含有する基が金属原子に結合した構造を有しており、ケイ素含有基が結合する金属原子としては、前述のＭ1～Ｍ3で表される金属原子として説明したものが挙げられる。ケイ素含有基としては、具体的に、－Ｏ－ＳｉＲa3Ｒa4Ｒa5で表される基が好ましい。 The silicon-containing group-bonded metal represented by M 1 has a structure in which a silicon-containing group is bonded to a metal atom . Examples of the metal atom represented by are those described above. Specifically, the silicon-containing group is preferably a group represented by --O--SiR a3 R a4 R a5 .
　Ｍ1で表されるオキシカルボニル含有基結合金属は、オキシカルボニルを含有する基が金属原子に結合した構造を有しており、オキシカルボニル含有基が結合する金属原子としては、前述のＭ1～Ｍ3で表される金属原子として説明したものが挙げられる。オキシカルボニル含有基としては、具体的に、－ＯＣ（＝Ｏ）Ｒa13で表される基が好ましい。 The oxycarbonyl-containing group-bonded metal represented by M 1 has a structure in which an oxycarbonyl-containing group is bonded to a metal atom. Examples of the metal atom represented by M 3 include those described above. Specifically, the oxycarbonyl-containing group is preferably a group represented by -OC(=O)R a13 .
　Ｍ1で表されるオキシスルホニル含有基結合金属は、オキシスルホニルを含有する基が金属原子に結合した構造を有しており、オキシスルホニル含有基が結合する金属原子としては、前述のＭ1～Ｍ3で表される金属原子として説明したものが挙げられる。オキシスルホニル含有基としては、具体的に、－ＯＳ（＝Ｏ）2Ｒa14で表される基が好ましい。 The oxysulfonyl-containing group-bonded metal represented by M 1 has a structure in which an oxysulfonyl-containing group is bonded to a metal atom. Examples of the metal atom represented by M 3 include those described above. Specifically, the oxysulfonyl-containing group is preferably a group represented by -OS(=O) 2 R a14 .
　Ｍ1は、Ｃｕ、Ｎｉ、ＺｎまたはＡｌ；これらの酸化物；これらの水酸化物；これらのハロゲン化物；これらにリン含有基が結合した構造；これらにケイ素含有基が結合した構造；これらにオキシカルボニル含有基が結合した構造；或いは、これらにオキシスルホニル含有基が結合した構造であることが好ましく、
　Ｃｕ；Ｎｉ；Ｚｎ；Ａｌ；ＡｌＯＨ；ＡｌＣｌ；ＺｒＣｌ；－ＯＰ（＝Ｏ）Ｒa1Ｒa2が結合したＣｕ、Ｎｉ、ＺｎまたはＡｌ；－Ｏ－ＳｉＲa3Ｒa4Ｒa5が結合したＣｕ、Ｎｉ、ＺｎまたはＡｌ；－ＯＣ（＝Ｏ）Ｒa13が結合したＣｕ、Ｎｉ、ＺｎまたはＡｌ；或いは－ＯＳ（＝Ｏ）2Ｒa14が結合したＣｕ、Ｎｉ、ＺｎまたはＡｌであることがより好ましく、
　Ｚｎ、ＡｌＯＨ、ＡｌＣｌ、－ＯＰ（＝Ｏ）Ｒa1Ｒa2が結合したＡｌ、－Ｏ－ＳｉＲa3Ｒa4Ｒa5が結合したＡｌ、－ＯＣ（＝Ｏ）Ｒa13が結合したＡｌ、または－ＯＳ（＝Ｏ）2Ｒa14が結合したＡｌであることがさらに好ましく、
　Ｚｎ、ＡｌＯＨ、または－ＯＰ（＝Ｏ）Ｒa1Ｒa2が結合したＡｌであることが特に好ましい。 M 1 is Cu, Ni, Zn or Al; their oxides; their hydroxides; their halides; A structure in which an oxycarbonyl-containing group is bonded; or a structure in which an oxysulfonyl-containing group is bonded to these,
Cu; Ni ; Zn ; Al; AlOH ; AlCl; ZrCl ; , Zn or Al; Cu, Ni, Zn or Al to which —OC(=O)R a13 is attached; or Cu, Ni, Zn or Al to which —OS(=O) 2 R a14 is attached. ,
Zn, AlOH, AlCl, Al with -OP(=O)R a1 R a2 attached, Al with -O-SiR a3 R a4 R a5 attached, Al with -OC(=O) R a13 attached, or - More preferably, OS(=O) 2 R a14 is Al to which
Particularly preferred are Zn, AlOH, or Al with -OP(=O)R a1 R a2 attached.
　Ｍ2及びＭ3は同一であっても異なっていてもよいが、同一であることが好ましい。 M 2 and M 3 may be the same or different, but are preferably the same.
　Ｍ2及びＭ3は、それぞれ独立して、Ｃｕ、Ｎｉ、ＺｎまたはＡｌ；これらの酸化物；これらの水酸化物；これらのハロゲン化物であることが好ましく、
　それぞれ独立して、Ｃｕ、Ｎｉ、ＺｎまたはＡｌであることがより好ましい。 M 2 and M 3 are each independently preferably Cu, Ni, Zn or Al; oxides thereof; hydroxides thereof; halides thereof;
More preferably, they are Cu, Ni, Zn or Al each independently.
　本発明の着色剤として含まれるフタロシアニン化合物は、アルミフタロシアニン化合物であることが好ましい。アルミフタロシアニン化合物とは、フタロシアニン骨格を有し、該フタロシアニン骨格とアルミニウムとが錯体を形成している化合物をいう。アルミフタロシアニン化合物は、具体的には、式（Ｘａ）又は式（Ｘｂ）で表される化合物であることが好ましい。 The phthalocyanine compound contained as the coloring agent of the present invention is preferably an aluminum phthalocyanine compound. An aluminum phthalocyanine compound is a compound having a phthalocyanine skeleton and forming a complex between the phthalocyanine skeleton and aluminum. Specifically, the aluminum phthalocyanine compound is preferably a compound represented by Formula (Xa) or Formula (Xb).
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
［式（Ｘａ）中、
　Ｚは、ヒドロキシ基、塩素原子、－ＯＰ（＝Ｏ）Ｒa1Ｒa2、－Ｏ－ＳｉＲa3Ｒa4Ｒa5、－ＯＣ（＝Ｏ）Ｒa13、又は－ＯＳ（＝Ｏ）2Ｒa14を表す。
　Ｒa1～Ｒa5及びＲa13～Ｒa14は、それぞれ独立に、水素原子、ヒドロキシ基、置換基を有していてもよい炭素数１～２０の炭化水素基、又は置換基を有していてもよい炭素数１～２０の複素環基を表し、Ｒa1とＲa2、またはＲa3～Ｒa5のいずれか二つは、互いに結合して環を形成してもよい。該炭化水素基の炭素数が２～２０であり且つ該炭化水素基が－ＣＨ2－を有する場合、該－ＣＨ2－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わっていてもよい。
　Ｘx1～Ｘx4及びｎｘ１～ｎｘ４は、前記に同じ。
式（Ｘｂ）中、
　Ｌ、Ｘx5～Ｘx12及びｎｘ５～ｎｘ１２は、前記に同じ。］ [in the formula (Xa),
Z is a hydroxy group, a chlorine atom, -OP(=O)R a1 R a2 , -O-SiR a3 R a4 R a5 , -OC(=O) R a13 or -OS(=O) 2 R a14 show.
R a1 to R a5 and R a13 to R a14 each independently have a hydrogen atom, a hydroxy group, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or a substituent; any two of R a1 and R a2 or R a3 to R a5 may combine to form a ring. When the hydrocarbon group has 2 to 20 carbon atoms and has —CH 2 —, the —CH 2 — may be replaced with —O—, —S— or —CO—. good.
X x1 to X x4 and nx1 to nx4 are the same as above.
In formula (Xb),
L, X x5 to X x12 and nx5 to nx12 are the same as above. ]
　式（Ｘａ）において、
　Ｚは、好ましくはヒドロキシ基又は－ＯＰ（＝Ｏ）Ｒa1Ｒa2である。
　Ｒa1は、好ましくは－Ｒb1、－Ｏ－Ｒb1、－Ｓ－Ｒb1、又は－ＣＯ－Ｒb1である。
　Ｒa2は、好ましくは－Ｒb2、－Ｏ－Ｒb2、－Ｓ－Ｒb2、又は－ＣＯ－Ｒb2である。
　Ｒb1及びＲb2は、置換基を有していてもよい炭素数１～２０の炭化水素基を表し、Ｒb1及びＲb2は、互いに結合して環を形成してもよい。 In formula (Xa),
Z is preferably a hydroxy group or -OP(=O)R a1 R a2 .
R a1 is preferably -R b1 , -OR b1 , -SR b1 or -CO-R b1 .
R a2 is preferably -R b2 , -OR b2 , -SR b2 or -CO-R b2 .
R b1 and R b2 represent optionally substituted hydrocarbon groups having 1 to 20 carbon atoms, and R b1 and R b2 may combine with each other to form a ring.
　式（Ｘｂ）において、
　Ｌは、好ましくは－Ｏ－Ｐ（＝Ｏ）Ｒa12－Ｏ－である。
　Ｒa12は、好ましくは－Ｒb3、－Ｏ－Ｒb3、－Ｓ－Ｒb3、又は－ＣＯ－Ｒb3である。
　Ｒb3は、置換基を有していてもよい炭素数１～２０の炭化水素基を表す。 In formula (Xb),
L is preferably -OP(=O)R a12 -O-.
R a12 is preferably -R b3 , -OR b3 , -SR b3 or -CO-R b3 .
R b3 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
　前記式（Ｘａ）で表される化合物は、式（Ｘ０）又は式（ＸＩ）で表される化合物であることが好ましい。また、前記式（Ｘｂ）で表される化合物は、式（ＸＩＩ）で表される化合物であることが好ましい。以下、式（Ｘ０）、式（ＸＩ）又は式（ＸＩＩ）で表される化合物の部分構造を挙げて本発明をより具体的に説明する。 The compound represented by formula (Xa) is preferably a compound represented by formula (X0) or formula (XI). Moreover, the compound represented by the formula (Xb) is preferably a compound represented by the formula (XII). Hereinafter, the present invention will be described more specifically with partial structures of the compounds represented by formula (X0), formula (XI), or formula (XII).
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
［式（ＸＩ）中、
　Ｒx1は、置換基を有していてもよい炭素数２～２０の脂肪族不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の芳香族炭化水素基を表し、Ｒx2は、水素原子、置換基を有していてもよい炭素数１～２０の炭化水素基、又はＺx2とＲx1とを結ぶ単結合を表す。
　Ｚx1及びＺx2は、それぞれ独立に、単結合又は酸素原子を表す。
式（Ｘ０）及び式（ＸＩ）中、
　Ｘx1～Ｘx4、ｎｘ１～ｎｘ４は、前記に同じ。
式（ＸＩＩ）中、
　Ｒx3は、置換基を有していてもよい炭素数２～２０の脂肪族不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の芳香族炭化水素基を表す。
　Ｚx3は、単結合又は酸素原子を表す。
　Ｘx5～Ｘx12、ｎｘ５～ｎｘ１２は、前記に同じ。］ [in the formula (XI),
R x1 represents an optionally substituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, R x2 represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or a single bond connecting Z x2 and R x1 .
Z x1 and Z x2 each independently represent a single bond or an oxygen atom.
In formula (X0) and formula (XI),
X x1 to X x4 and nx1 to nx4 are the same as above.
In formula (XII),
R x3 represents an optionally substituted C 2-20 aliphatic unsaturated hydrocarbon group or an optionally substituted C 6-20 aromatic hydrocarbon group.
Z x3 represents a single bond or an oxygen atom.
X x5 to X x12 and nx5 to nx12 are the same as above. ]
　また前記フタロシアニン化合物は、式（ＹＩ）又は式（ＹＩＩ）で表される化合物であることも好ましい。以下、式（ＹＩ）又は式（ＹＩＩ）で表される化合物の部分構造を挙げて本発明をより具体的に説明する。 The phthalocyanine compound is also preferably a compound represented by formula (YI) or formula (YII). Hereinafter, the present invention will be described more specifically with partial structures of the compounds represented by formula (YI) or formula (YII).
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
［式（ＹＩ）中、
　Ｒy1は、水素原子又は置換基を有していてもよい炭素数１～２０の炭化水素基を表す。
　Ｒy2は、水素原子、置換基を有していてもよい炭素数１～２０の炭化水素基又はＺy3とＲy1とを結ぶ単結合を表す。
　Ｙ1及びＺy1は、それぞれ独立に、酸素原子又は硫黄原子を表す。
　Ｚy2及びＺy3は、それぞれ独立に、単結合、酸素原子又は硫黄原子を表す。
　ただし、Ｙ1、Ｚy1、Ｚy2及びＺy3のうち少なくとも１つは硫黄原子を表す。
　Ｘy1～Ｘy4は、それぞれ独立に、－Ｒy4、－ＯＲy4、－ＳＲy4、－ＳＯ3Ｈ、－ＳＯ3 -Ｍ+、－ＳＯ3Ｒy10、－ＳＯ2ＮＲy11Ｒy12、ハロゲン原子、又はニトロ基を表す。
　Ｒy4は、置換基を有していてもよい炭素数１～２０の炭化水素基を表す。
　Ｍ+は、+Ｎ（Ｒy13）4又はアルカリ金属イオンを表し、Ｒy13は、それぞれ独立に、水素原子又は炭素数１～２０の炭化水素基を表す。
　Ｒy10は、炭素数１～２０の飽和炭化水素基を表す。
　Ｒy11及びＲy12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１～２０の炭化水素基を表す。
　ｎｙ１～ｎｙ４は、それぞれ独立に、０～４の整数を表す。
式（ＹＩＩ）中、
　Ｒy3は、水素原子又は置換基を有していてもよい炭素数１～２０の炭化水素基を表す。
　Ｙ2及びＺy4は、それぞれ独立に、酸素原子又は硫黄原子を表す。
　Ｚy5は、単結合、酸素原子又は硫黄原子を表す。
　ただし、Ｙ2、Ｚy4及びＺy5のうち少なくとも１つは硫黄原子を表す。
　Ｘy5～Ｘy12は、それぞれ独立に、－Ｒy5、－ＯＲy5、－ＳＲy5、－ＳＯ3Ｈ、－ＳＯ3 -Ｗ+、－ＳＯ3Ｒy14、－ＳＯ2ＮＲy15Ｒy16、ハロゲン原子、又はニトロ基を表す。
　Ｒy5は、置換基を有していてもよい炭素数１～２０の炭化水素基を表す。
　Ｗ+は、+Ｎ（Ｒy17）4又はアルカリ金属イオンを表し、Ｒy17は、それぞれ独立に、水素原子又は炭素数１～２０の炭化水素基を表す。
　Ｒy14は、炭素数１～２０の飽和炭化水素基を表す。
　Ｒy15及びＲy16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１～２０の炭化水素基を表す。
　ｎｙ５～ｎｙ１２は、それぞれ独立に、０～４の整数を表す。］ [In the formula (YI),
R y1 represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
R y2 represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or a single bond connecting Z y3 and R y1 .
Y 1 and Z y1 each independently represent an oxygen atom or a sulfur atom.
Zy2 and Zy3 each independently represent a single bond, an oxygen atom or a sulfur atom.
However, at least one of Y1 , Zy1 , Zy2 and Zy3 represents a sulfur atom.
X y1 to X y4 each independently represent -R y4 , -OR y4 , -SR y4 , -SO 3 H, -SO 3 - M + , -SO 3 R y10 , -SO 2 NR y11 R y12 , halogen represents an atom or a nitro group.
R y4 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
M + represents + N(R y13 ) 4 or an alkali metal ion, and each R y13 independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
R y10 represents a saturated hydrocarbon group having 1 to 20 carbon atoms.
R y11 and R y12 each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
ny1 to ny4 each independently represent an integer of 0 to 4;
In formula (YII),
R y3 represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
Y2 and Zy4 each independently represent an oxygen atom or a sulfur atom.
Zy5 represents a single bond, an oxygen atom or a sulfur atom.
However, at least one of Y2 , Zy4 and Zy5 represents a sulfur atom.
X y5 to X y12 are each independently -R y5 , -OR y5 , -SR y5 , -SO 3 H, -SO 3 - W + , -SO 3 R y14 , -SO 2 NR y15 R y16 , halogen represents an atom or a nitro group.
R y5 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
W + represents + N(R y17 ) 4 or an alkali metal ion, and each R y17 independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
R y14 represents a saturated hydrocarbon group having 1 to 20 carbon atoms.
R y15 and R y16 each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
ny5 to ny12 each independently represent an integer of 0 to 4; ]
　なお、式（ＹＩ）で表される化合物には、式（ＹＩａ）で表される共鳴構造を有する化合物、又は式（ＹＩｂ）で表される平衡関係にある化合物が含まれ、式（ＹＩＩ）で表される化合物には、式（ＹＩＩａ)で表される共鳴構造を有する化合物、又は式（ＹＩＩｂ）で表される平衡関係にある化合物が含まれる。 The compound represented by formula (YI) includes a compound having a resonance structure represented by formula (YIa) or a compound represented by formula (YIb) in equilibrium, and formula (YII) The compound represented by includes a compound having a resonance structure represented by formula (YIIa) or a compound represented by formula (YIIb) having an equilibrium relationship.
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
［式（ＹＩ）、式（ＹＩａ）及び式（ＹＩｂ）中、
　Ｒy1、Ｒy2、Ｙ1、Ｚy1、Ｚy2、Ｚy3、Ｘy1～Ｘy4、及びｎｙ１～ｎｙ４は、前記に同じ。
式（ＹＩＩ）、式（ＹＩＩａ）及び式（ＹＩＩｂ）中、
　Ｒy3、Ｙ2、Ｚy4、Ｚy5、Ｘy5～Ｘy12、及びｎｙ５～ｎｙ１２は、前記に同じ。］ [In Formula (YI), Formula (YIa) and Formula (YIb),
R y1 , R y2 , Y 1 , Z y1 , Z y2 , Z y3 , X y1 to X y4 and ny1 to ny4 are the same as above.
In formula (YII), formula (YIIa) and formula (YIIb),
R y3 , Y 2 , Z y4 , Z y5 , X y5 to X y12 and ny5 to ny12 are the same as above. ]
　Ｒx1及びＲx3で表される脂肪族不飽和炭化水素基の炭素数は、２～２０であり、より好ましくは２～１０であり、さらに好ましくは２～７であり、特に好ましくは２～５である。 The aliphatic unsaturated hydrocarbon group represented by R x1 and R x3 has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 2 to 7 carbon atoms, and particularly preferably 2 to 5.
　Ｒx1及びＲx3で表される脂肪族不飽和炭化水素基は、鎖状又は環状（脂環式炭化水素基）であってもよい。 The aliphatic unsaturated hydrocarbon groups represented by R x1 and R x3 may be chain or cyclic (alicyclic hydrocarbon groups).
　Ｒx1及びＲx3で表される不飽和鎖状炭化水素基は、直鎖状であっても分枝鎖状であってもよく、具体的には、
　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。 The unsaturated chain hydrocarbon groups represented by R x1 and R x3 may be linear or branched, and specifically:
Ethenyl group (vinyl group), propenyl group (e.g., 1-propenyl group, 2-propenyl group (allyl group)), 1-methylethenyl group, butenyl group (e.g., 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 (e.g., 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group), 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 ( 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, alkenyl groups such as an octadecenyl group, a nonadecenyl group, and an 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-heptynyl group), 1-ethyl-3-pentynyl group, octynyl group (e.g., 1-octynyl group, 2-octynyl group, 7-octynyl group ), nonynyl group (e.g., 2-nonynyl group, 8-nonynyl group), decynyl group (e.g., 2-decynyl group, 9-decynyl group), undecynyl group, dodecynyl group, tridecynyl group, tetradecynyl group, pentadecynyl group, hexadecynyl alkynyl groups such as groups, heptadecynyl groups, octadecynyl groups, nonadecynyl groups and icosinyl groups;
etc.
　Ｒx1及びＲx3で表される不飽和脂環式炭化水素基としては、
　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；
　ノルボルネニル基等の不飽和多環式炭化水素基；
等が挙げられる。 Examples of unsaturated alicyclic hydrocarbon groups represented by R x1 and R x3 include:
Cycloalkenyl groups such as cyclohexenyl group (e.g., cyclohex-1-en-1-yl group, cyclohex-2-en-1-yl group, cyclohex-3-en-1-yl group), cycloheptenyl group and cyclooctenyl group ;
unsaturated polycyclic hydrocarbon groups such as norbornenyl groups;
etc.
　Ｒx1及びＲx3で表される炭素数２～２０の脂肪族不飽和炭化水素基は置換基を有していてもよい。
　Ｒx1及びＲx3で表される炭素数２～２０の脂肪族不飽和炭化水素基の置換基としては、置換基を有していてもよい炭素数６～２０の芳香族炭化水素基、置換基を有していてもよい複素環基、ハロゲン原子、ニトロ基、シアノ基、－ＯＲxa1、－ＣＯ2Ｒxa1、－ＳＲxa1、－ＳＯ3Ｒxa1、－ＳＯ2ＮＲxa1Ｒxa2及び－ＮＲxa1Ｒxa2等が挙げられる。
　ここで、Ｒxa1及びＲxa2は、それぞれ独立に、水素原子又は炭素数１～２０の炭化水素基を表す。Ｒxa1及びＲxa2で表される炭素数１～２０の炭化水素基は、後述するＲb1～Ｒb3、Ｒx2、Ｒx4、Ｒx5及びＲy1～Ｒy5等で表される炭素数１～２０の炭化水素基と同じである。
　なお、前記脂肪族不飽和炭化水素基が置換基として芳香族炭化水素基を有する場合、脂肪族不飽和炭化水素基の炭素数と置換基としての芳香族炭化水素基の炭素数の合計が２０以下となることが好ましい。 The aliphatic unsaturated hydrocarbon groups having 2 to 20 carbon atoms represented by R x1 and R x3 may have a substituent.
Substituents for the aliphatic unsaturated hydrocarbon groups having 2 to 20 carbon atoms represented by R x1 and R x3 include aromatic hydrocarbon groups having 6 to 20 carbon atoms which may be substituted, substituted a heterocyclic group optionally having a group, a halogen atom, a nitro group, a cyano group, —OR xa1 , —CO 2 R xa1 , —SR xa1 , —SO 3 R xa1 , —SO 2 NR xa1 R xa2 and — NR xa1 R xa2 and the like.
Here, R xa1 and R xa2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon groups having 1 to 20 carbon atoms represented by R xa1 and R xa2 are 1 carbon atoms represented by R b1 to R b3 , R x2 , R x4 , R x5 and R y1 to R y5 described later. ∼20 hydrocarbon groups.
When the aliphatic unsaturated hydrocarbon group has an aromatic hydrocarbon group as a substituent, the total carbon number of the aliphatic unsaturated hydrocarbon group and the aromatic hydrocarbon group as a substituent is 20. It is preferable that:
　Ｒx1及びＲx3で表される炭素数２～２０の脂肪族不飽和炭化水素基の置換基として用いられる炭素数６～２０の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が挙げられる。
　該芳香族炭化水素基の炭素数は、好ましくは６～１０であり、より好ましくは６～８である。
　該芳香族炭化水素基は置換基を有していてもよく、置換基としては、ハロゲン原子、ニトロ基、シアノ基、－ＯＲxa1、－ＣＯ2Ｒxa1、－ＳＲxa1、－ＳＯ3Ｒxa1、－ＳＯ2ＮＲxa1Ｒxa2及び－ＮＲxa1Ｒxa2等が挙げられる（ただし、Ｒxa1及びＲxa2は前記に同じ）。 The aromatic hydrocarbon group having 6 to 20 carbon atoms used as a substituent for the unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms represented by R x1 and R x3 includes:
phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 4-vinylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, o-tert-butylphenyl group, m-tert-butylphenyl group, p-tert-butylphenyl group, 3,5-di(tert-butyl)phenyl group, 3,5-di (tert-butyl)-4-methylphenyl group, 4-butylphenyl group, 4-pentylphenyl group, 2,6-bis(1-methylethyl)phenyl group, 2,4,6-tris(1-methylethyl ) phenyl group, 4-cyclohexylphenyl group, 2,4,6-trimethylphenyl group, 4-octylphenyl group, 4-(1,1,3,3-tetramethylbutyl)phenyl group, 1-naphthyl group, 2 -naphthyl group, 6-methyl-2-naphthyl group, 5,6,7,8-tetrahydro-1-naphthyl group, 5,6,7,8-tetrahydro-2-naphthyl group, fluorenyl group, phenanthryl group, anthryl group, 2-dodecylphenyl group, 3-dodecylphenyl group, 4-dodecylphenyl group, perylenyl group, chrysenyl group and pyrenyl group.
The aromatic hydrocarbon group preferably has 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms.
The aromatic hydrocarbon group may have a substituent, and examples of the substituent include a halogen atom, a nitro group, a cyano group, —OR xa1 , —CO 2 R xa1 , —SR xa1 and —SO 3 R xa1 . , —SO 2 NR xa1 R xa2 and —NR xa1 R xa2 (provided that R xa1 and R xa2 are the same as above).
　Ｒx1及びＲx3で表される炭素数２～２０の脂肪族不飽和炭化水素基の置換基として用いられる複素環基は、単環であってもよいし多環であってもよく、好ましくは環の構成要素としてヘテロ原子を含む複素環である。ヘテロ原子としては、窒素原子、酸素原子及び硫黄原子等が挙げられる。
　窒素原子のみをヘテロ原子として含む複素環としては、アジリジン、アゼチジン、ピロリジン、ピペリジン、ピペラジン等の単環系飽和複素環；ピロール、ピラゾール、イミダゾール、１，２，３－トリアゾール、１，２，４－トリアゾール等の５員環系不飽和複素環、ピリジン、ピリダジン、ピリミジン、ピラジン、１，３，５－トリアジン等の６員環系不飽和複素環等の単環系不飽和複素環；インダゾール、インドリン、イソインドリン、イソインドリン－１，３－ジオン、インドール、インドリジン、ベンゾイミダゾール、キノリン、イソキノリン、キノキサリン、キナゾリン、シンノリン、フタラジン、ナフチリジン、プリン、プテリジン、ベンゾピラゾール、ベンゾピペリジン等の縮合二環系複素環；カルバゾール、アクリジン、フェナジン等の縮合三環系複素環；等が挙げられる。
　酸素原子のみをヘテロ原子として含む複素環としては、オキシラン、オキセタン、テトラヒドロフラン、テトラヒドロピラン、１，３－ジオキサン、１，４－ジオキサン等の単環系飽和複素環；１，４－ジオキサスピロ［４．５］デカン、１，４－ジオキサスピロ［４．５］ノナン等の二環系飽和複素環；α－アセトラクトン、β－プロピオラクトン、γ－ブチロラクトン、δ－バレロラクトン等のラクトン系複素環；フラン等の５員環系不飽和複素環、２Ｈ－ピラン、４Ｈ－ピラン等の６員環系不飽和複素環等の単環系不飽和複素環；１－ベンゾフラン、ベンゾピラン、ベンゾジオキソール、クロマン、イソクロマン等の縮合二環系複素環；キサンテン、ジベンゾフラン等の縮合三環系複素環；等が挙げられる。
　硫黄原子のみをヘテロ原子として含む複素環としては、ジチオラン等の５員環系飽和複素環、チアン、１，３－ジチアン等の６員環系飽和複素環等の単環系飽和複素環；チオフェン等の５員環系不飽和複素環、４Ｈ－チオピラン等の６員環系不飽和複素環等の単環系不飽和複素環；ベンゾテトラヒドロチオピラン等のベンゾチオピラン、ベンゾチオフェン等の縮合二環系複素環；チアントレン、ジベンゾチオフェン等の縮合三環系複素環；等が挙げられる。
　窒素原子及び酸素原子をヘテロ原子として含む複素環としては、モルホリン、２－ピロリドン、２－ピペリドン等の単環系飽和複素環；オキサゾール、イソオキサゾール等の単環系不飽和複素環；ベンゾオキサゾール、ベンゾイソオキサゾール、ベンゾオキサジン、ベンゾジオキサン、ベンゾイミダゾリン等の縮合二環系複素環；フェノキサジン等の縮合三環系複素環；等が挙げられる。
　窒素原子及び硫黄原子をヘテロ原子として含む複素環としては、チアゾール等の単環系不飽和複素環；ベンゾチアゾール等の縮合二環系複素環；フェノチアジン等の縮合三環系複素環；等が挙げられる。
　該複素環基の炭素数は、好ましくは２～３０であり、より好ましくは３～２２であり、さらに好ましくは３～２０である。
　該複素環基は置換基を有していてもよく、置換基としては、ハロゲン原子、ニトロ基、シアノ基、－ＯＲxa1、－ＣＯ2Ｒxa1、－ＳＲxa1、－ＳＯ3Ｒxa1、－ＳＯ2ＮＲxa1Ｒxa2及び－ＮＲxa1Ｒxa2等が挙げられる（ただし、Ｒxa1及びＲxa2は前記に同じ）。
　なお、該複素環の結合位は、各環に含まれる任意の水素原子が脱離した部分である。 The heterocyclic group used as a substituent of the unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms represented by R x1 and R x3 may be monocyclic or polycyclic, preferably is a heterocyclic ring containing a heteroatom as a ring member. Heteroatoms include nitrogen, oxygen and sulfur atoms.
Heterocyclic rings containing only nitrogen atoms as heteroatoms include monocyclic saturated heterocyclic rings such as aziridine, azetidine, pyrrolidine, piperidine and piperazine; pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4 - Monocyclic unsaturated heterocycles such as 5-membered unsaturated heterocycles such as triazole, 6-membered unsaturated heterocycles such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine; Condensed bicyclic rings such as indoline, isoindoline, isoindoline-1,3-dione, indole, indolizine, benzimidazole, quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, phthalazine, naphthyridine, purine, pteridine, benzopyrazole, benzopiperidine, etc. system heterocycles; condensed tricyclic heterocycles such as carbazole, acridine, and phenazine;
Heterocyclic rings containing only oxygen atoms as heteroatoms include monocyclic saturated heterocyclic rings such as oxirane, oxetane, tetrahydrofuran, tetrahydropyran, 1,3-dioxane and 1,4-dioxane; 1,4-dioxaspiro [4. 5] Bicyclic saturated heterocycles such as decane and 1,4-dioxaspiro[4.5]nonane; Lactone heterocycles such as α-acetolactone, β-propiolactone, γ-butyrolactone and δ-valerolactone; monocyclic unsaturated heterocycles such as 5-membered unsaturated heterocyclic rings such as furan, 2H-pyran, 6-membered unsaturated heterocyclic rings such as 4H-pyran; 1-benzofuran, benzopyran, benzodioxole, condensed bicyclic heterocycles such as chroman and isochroman; condensed tricyclic heterocycles such as xanthene and dibenzofuran; and the like.
The heterocyclic ring containing only a sulfur atom as a heteroatom includes a 5-membered saturated heterocyclic ring such as dithiolane, a monocyclic saturated heterocyclic ring such as a 6-membered saturated heterocyclic ring such as thiane and 1,3-dithiane; monocyclic unsaturated heterocycles such as 5-membered unsaturated heterocycles such as 4H-thiopyran; benzothiopyrans such as benzotetrahydrothiopyran; condensed bicyclic systems such as benzothiophene heterocycles; condensed tricyclic heterocycles such as thianthrene and dibenzothiophene;
Heterocyclic rings containing a nitrogen atom and an oxygen atom as heteroatoms include monocyclic saturated heterocyclic rings such as morpholine, 2-pyrrolidone and 2-piperidone; monocyclic unsaturated heterocyclic rings such as oxazole and isoxazole; Condensed bicyclic heterocycles such as benzoisoxazole, benzoxazine, benzodioxane and benzimidazoline; condensed tricyclic heterocycles such as phenoxazine; and the like.
Heterocyclic rings containing a nitrogen atom and a sulfur atom as heteroatoms include monocyclic unsaturated heterocyclic rings such as thiazole; condensed bicyclic heterocyclic rings such as benzothiazole; condensed tricyclic heterocyclic rings such as phenothiazine; be done.
The heterocyclic group preferably has 2 to 30 carbon atoms, more preferably 3 to 22 carbon atoms, and still more preferably 3 to 20 carbon atoms.
The heterocyclic group may have a substituent, and examples of the substituent include a halogen atom, a nitro group, a cyano group, —OR xa1 , —CO 2 R xa1 , —SR xa1 , —SO 3 R xa1 , — SO 2 NR xa1 R xa2 and -NR xa1 R xa2 (provided that R xa1 and R xa2 are the same as above).
In addition, the bonding position of the heterocyclic ring is a portion from which any hydrogen atom contained in each ring is eliminated.
　Ｒx1及びＲx3で表される炭素数２～２０の脂肪族不飽和炭化水素基の置換基として用いられるハロゲン原子は、フッ素原子、塩素原子、臭素原子及びヨウ素原子等が例示される。 Halogen atoms used as substituents of the aliphatic unsaturated hydrocarbon groups having 2 to 20 carbon atoms represented by R x1 and R x3 are exemplified by fluorine, chlorine, bromine and iodine atoms.
　Ｒx1及びＲx3で表される芳香族炭化水素基の炭素数は、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であり、特に好ましくは６である。 The aromatic hydrocarbon group represented by R x1 and R x3 has 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, still more preferably 6 to 8 carbon atoms, and particularly preferably 6 carbon atoms.
　Ｒx1及びＲx3で表される芳香族炭化水素基としては、Ｒx1及びＲx3で表される炭素数２～２０の脂肪族不飽和炭化水素基の置換基として用いられる炭素数６～２０の芳香族炭化水素基として例示した芳香族炭化水素基等が挙げられる。 The aromatic hydrocarbon group represented by R x1 and R x3 includes 6 to 20 carbon atoms used as substituents for the aliphatic unsaturated hydrocarbon groups of 2 to 20 carbon atoms represented by R x1 and R x3 . and the aromatic hydrocarbon groups exemplified as the aromatic hydrocarbon groups of .
　Ｒx1及びＲx3で表される炭素数６～２０の芳香族炭化水素基は置換基を有していてもよい。
　Ｒx1及びＲx3で表される炭素数６～２０の芳香族炭化水素基の置換基としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子等のハロゲン原子、ニトロ基、シアノ基、－ＯＲxa1、－ＣＯ2Ｒxa1、－ＳＲxa1、－ＳＯ3Ｒxa1、－ＳＯ2ＮＲxa1Ｒxa2及び－ＮＲxa1Ｒxa2等が挙げられる（ただし、Ｒxa1及びＲxa2は前記に同じ）。 The aromatic hydrocarbon groups having 6 to 20 carbon atoms represented by R x1 and R x3 may have a substituent.
Examples of substituents of the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R x1 and R x3 include halogen atoms such as fluorine, chlorine, bromine and iodine atoms, nitro group, cyano group, -OR xa1 , —CO 2 R xa1 , —SR xa1 , —SO 3 R xa1 , —SO 2 NR xa1 R xa2 and —NR xa1 R xa2 (provided that R xa1 and R xa2 are the same as above).
　Ｒa1～Ｒa14、Ｒb1～Ｒb3、Ｒx2、Ｒx4、Ｒx5、Ｒx11～Ｒx13、Ｒx15～Ｒx17、Ｒy1～Ｒy5、Ｒy11～Ｒy13及びＲy15～Ｒy17で表される炭化水素基の炭素数は、１～２０であり、より好ましくは１～１５である。 R a1 to R a14 , R b1 to R b3 , R x2 , R x4 , R x5 , R x11 to R x13 , R x15 to R x17 , R y1 to R y5 , R y11 to R y13 and R y15 to R y17 The number of carbon atoms in the hydrocarbon group represented by is 1 to 20, preferably 1 to 15.
　Ｒa1～Ｒa14、Ｒb1～Ｒb3、Ｒx2、Ｒx4、Ｒx5、Ｒx11～Ｒx13、Ｒx15～Ｒx17、Ｒy1～Ｒy5、Ｒy11～Ｒy13及びＲy15～Ｒy17で表される炭素数１～２０の炭化水素基は、脂肪族炭化水素基であっても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。 R a1 to R a14 , R b1 to R b3 , R x2 , R x4 , R x5 , R x11 to R x13 , R x15 to R x17 , R y1 to R y5 , R y11 to R y13 and R y15 to R y17 The hydrocarbon group having 1 to 20 carbon atoms represented by may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group is saturated or unsaturated. may be linear or cyclic (alicyclic hydrocarbon group).
　Ｒa1～Ｒa14、Ｒb1～Ｒb3、Ｒx2、Ｒx4、Ｒx5、Ｒx11～Ｒx13、Ｒx15～Ｒx17、Ｒy1～Ｒy5、Ｒy11～Ｒy13及びＲy15～Ｒy17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、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基、ｎ－ウンデシル基、ｎ－ドデシル基、ｎ－トリデシル基、ｎ－テトラデシル基、ｎ－ペンタデシル基、ｎ－ヘキサデシル基、ｎ－ヘプタデシル基、ｎ－オクタデシル基、ｎ－ノナデシル基、及びｎ－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、１，１，２－トリメチルプロピル基、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。
　Ｒa1～Ｒa14、Ｒb1～Ｒb3、Ｒx2、Ｒx4、Ｒx5、Ｒx11～Ｒx13、Ｒx15～Ｒx17、Ｒy1～Ｒy5、Ｒy11～Ｒy13及びＲy15～Ｒy17で表される飽和鎖状炭化水素基の炭素数は、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～Ｒa14、Ｒb1～Ｒb3、Ｒx2、Ｒx4、Ｒx5、Ｒx11～Ｒx13、Ｒx15～Ｒx17、Ｒy1～Ｒy5、Ｒy11～Ｒy13及びＲy15～Ｒy17で表される不飽和鎖状炭化水素基の炭素数は、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。 R a1 to R a14 , R b1 to R b3 , R x2 , R x4 , R x5 , R x11 to R x13 , R x15 to R x17 , R y1 to R y5 , R y11 to R y13 and R y15 to R y17 As the saturated or unsaturated chain hydrocarbon group represented by
methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group , n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group. shaped alkyl 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-ethyl propyl group, 3-methylbutyl group, neopentyl group, 1,1-dimethylpropyl group, 1,1,2-trimethylpropyl 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-methylhexyl group, 5-methylhexyl group, 2-ethylhexyl group, 1-methylhexyl group, 1-ethylpentyl group, 1-propylbutyl group, 3-ethylheptyl group, 2,2-dimethylheptyl group, 1-methylheptyl group, 1-ethylhexyl group, 1-propylpentyl group, 1-methyloctyl group , 1-ethylheptyl, 1-propylhexyl, 1-butylpentyl, 1-methylnonyl, 1-ethyloctyl, 1-propylheptyl and 1-butylhexyl branched alkyl groups;
Ethenyl group (vinyl group), propenyl group (e.g., 1-propenyl group, 2-propenyl group (allyl group)), 1-methylethenyl group, butenyl group (e.g., 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 (e.g., 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group), 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 ( 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, alkenyl groups such as an octadecenyl group, a nonadecenyl group, and an 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-heptynyl group), 1-ethyl-3-pentynyl group, octynyl group (e.g., 1-octynyl group, 2-octynyl group, 7-octynyl group ), nonynyl group (e.g., 2-nonynyl group, 8-nonynyl group), decynyl group (e.g., 2-decynyl group, 9-decynyl group), undecynyl group, dodecynyl group, tridecynyl group, tetradecynyl group, pentadecynyl group, hexadecynyl alkynyl groups such as groups, heptadecynyl groups, octadecynyl groups, nonadecynyl groups and icosinyl groups;
etc.
R a1 to R a14 , R b1 to R b3 , R x2 , R x4 , R x5 , R x11 to R x13 , R x15 to R x17 , R y1 to R y5 , R y11 to R y13 and R y15 to R y17 The number of carbon atoms in the saturated chain hydrocarbon group represented by is preferably 1 to 10, more preferably 1 to 7, and still more preferably 1 to 5.
R a1 to R a14 , R b1 to R b3 , R x2 , R x4 , R x5 , R x11 to R x13 , R x15 to R x17 , R y1 to R y5 , R y11 to R y13 and R y15 to R y17 The number of carbon atoms in the unsaturated chain hydrocarbon group represented by is preferably 2 to 10, more preferably 2 to 7, and still more preferably 2 to 5.
　Ｒa1～Ｒa14、Ｒb1～Ｒb3、Ｒx2、Ｒx4、Ｒx5、Ｒx11～Ｒx13、Ｒx15～Ｒx17、Ｒy1～Ｒy5、Ｒy11～Ｒy13及びＲy15～Ｒy17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～Ｒa14、Ｒb1～Ｒb3、Ｒx2、Ｒx4、Ｒx5、Ｒx11～Ｒx13、Ｒx15～Ｒx17、Ｒy1～Ｒy5、Ｒy11～Ｒy13及びＲy15～Ｒy17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である。 R a1 to R a14 , R b1 to R b3 , R x2 , R x4 , R x5 , R x11 to R x13 , R x15 to R x17 , R y1 to R y5 , R y11 to R y13 and R y15 to R y17 As the saturated or unsaturated alicyclic hydrocarbon group represented by
cyclopropyl group, 1-methylcyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 1, 2-dimethylcyclohexyl group, 1,3-dimethylcyclohexyl group, 1,4-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6- dimethylcyclohexyl group, 3,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,2-dimethylcyclohexyl group, 3,3-dimethylcyclohexyl group, 4,4-dimethylcyclohexyl group, cyclooctyl group, 2, 4,6-trimethylcyclohexyl group, 2,2,6,6-tetramethylcyclohexyl group, 3,3,5,5-tetramethylcyclohexyl group, 4-pentylcyclohexyl group, 4-octylcyclohexyl group and 4-cyclohexylcyclohexyl group a cycloalkyl group such as a group;
Cycloalkenyl groups such as cyclohexenyl group (e.g., cyclohex-1-en-1-yl group, cyclohex-2-en-1-yl group, cyclohex-3-en-1-yl group), cycloheptenyl group and cyclooctenyl group ;
saturated or unsaturated polycyclic hydrocarbon groups such as norbornyl, norbornenyl, adamantyl and bicyclo[2.2.2]octyl groups;
etc.
R a1 to R a14 , R b1 to R b3 , R x2 , R x4 , R x5 , R x11 to R x13 , R x15 to R x17 , R y1 to R y5 , R y11 to R y13 and R y15 to R y17 The number of carbon atoms in the saturated or unsaturated alicyclic hydrocarbon group represented by is preferably 3-10.
　Ｒa1～Ｒa14、Ｒb1～Ｒb3、Ｒx2、Ｒx4、Ｒx5、Ｒx11～Ｒx13、Ｒx15～Ｒx17、Ｒy1～Ｒy5、Ｒy11～Ｒy13及びＲy15～Ｒy17で表される芳香族炭化水素基としては、Ｒx1及びＲx3で表される炭素数２～２０の脂肪族不飽和炭化水素基の置換基として用いられる炭素数６～２０の芳香族炭化水素基として例示した芳香族炭化水素基等が挙げられる。
　Ｒa1～Ｒa14、Ｒb1～Ｒb3、Ｒx2、Ｒx4、Ｒx5、Ｒx11～Ｒx13、Ｒx15～Ｒx17、Ｒy1～Ｒy5、Ｒy11～Ｒy13及びＲy15～Ｒy17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。 R a1 to R a14 , R b1 to R b3 , R x2 , R x4 , R x5 , R x11 to R x13 , R x15 to R x17 , R y1 to R y5 , R y11 to R y13 and R y15 to R y17 The aromatic hydrocarbon group represented by is an aromatic hydrocarbon having 6 to 20 carbon atoms used as a substituent for the aliphatic unsaturated hydrocarbon groups having 2 to 20 carbon atoms represented by R x1 and R x3 Examples of the group include the aromatic hydrocarbon groups exemplified.
R a1 to R a14 , R b1 to R b3 , R x2 , R x4 , R x5 , R x11 to R x13 , R x15 to R x17 , R y1 to R y5 , R y11 to R y13 and R y15 to R y17 The number of carbon atoms in the aromatic hydrocarbon group represented by is preferably 6-20, more preferably 6-10, still more preferably 6-8.
　Ｒa1～Ｒa14、Ｒb1～Ｒb3、Ｒx2、Ｒx4、Ｒx5、Ｒx11～Ｒx13、Ｒx15～Ｒx17、Ｒy1～Ｒy5、Ｒy11～Ｒy13及びＲy15～Ｒy17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、芳香族炭化水素基、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、（２－ナフチル）メチル基、及び９－フルオレニ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。 R a1 to R a14 , R b1 to R b3 , R x2 , R x4 , R x5 , R x11 to R x13 , R x15 to R x17 , R y1 to R y5 , R y11 to R y13 and R y15 to R y17 The hydrocarbon group represented by is a combination of the above-listed hydrocarbon groups (e.g., an aromatic hydrocarbon group and at least one of an aromatic hydrocarbon group, a chain hydrocarbon group and an alicyclic hydrocarbon group) may be a base,
benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2-ethylphenyl) methyl group, (3-ethylphenyl) methyl group, (4 -ethylphenyl)methyl group, (2-(tert-butyl)phenyl)methyl group, (3-(tert-butyl)phenyl)methyl group, (4-(tert-butyl)phenyl)methyl group, (3,5 -dimethylphenyl)methyl group, 1-phenylethyl group, 1-methyl-1-phenylethyl group, 1,1-diphenylethyl group, (1-naphthyl)methyl group, (2-naphthyl)methyl group, and 9- an aralkyl group such as a fluorenylmethyl group;
Arylalkenyl groups such as 1-phenylethenyl group, 2-phenylethenyl group (phenylvinyl group), 2,2-diphenylethenyl group, 2-phenyl-2-(1-naphthyl)ethenyl group;
arylalkynyl groups such as phenylethynyl groups;
a phenyl group to which one or more phenyl groups such as a biphenylyl group and a terphenylyl group are bonded;
A cyclohexylmethylphenyl group, a benzylphenyl group, a (dimethyl(phenyl)methyl)phenyl group and the like can be mentioned.
These carbon atoms are preferably 7-18, more preferably 7-15.
　Ｒa1～Ｒa14、Ｒb1～Ｒb3、Ｒx2、Ｒx4、Ｒx5、Ｒx11～Ｒx13、Ｒx15～Ｒx17、Ｒy1～Ｒy5、Ｒy11～Ｒy13及びＲy15～Ｒy17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。 R a1 to R a14 , R b1 to R b3 , R x2 , R x4 , R x5 , R x11 to R x13 , R x15 to R x17 , R y1 to R y5 , R y11 to R y13 and R y15 to R y17 The group represented by is a combination of the above-mentioned hydrocarbon groups (e.g., a chain hydrocarbon group and an alicyclic hydrocarbon group), such as a cyclopropylmethyl group, a cyclopropylethyl group, a cyclobutylmethyl cyclobutylethyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclohexylmethyl group, (2-methylcyclohexyl)methyl group, cyclohexylethyl group, adamantylmethyl group, etc. It may be an alkyl group.
These carbon atoms are preferably 4-15, more preferably 4-10.
　Ｒa1～Ｒa14、Ｒx4及びＲx5で表される炭化水素基の炭素数が２～２０であり且つ該炭化水素基が－ＣＨ2－を有する場合、該－ＣＨ2－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わっていてもよい。ただし、該炭素数２～２０の炭化水素基において、隣接する－ＣＨ2－が同時に－Ｏ－及び／又は－Ｓ－に置換されることはなく、末端の－ＣＨ2－が－Ｏ－、－Ｓ－又は－ＣＯ－に置換されることはない。 When the hydrocarbon group represented by R a1 to R a14 , R x4 and R x5 has 2 to 20 carbon atoms and the hydrocarbon group has —CH 2 —, the —CH 2 — is —O -, -S- or -CO- may be substituted. However, in the hydrocarbon group having 2 to 20 carbon atoms, adjacent —CH 2 — are not simultaneously substituted with —O— and/or —S—, and the terminal —CH 2 — is —O—, -S- or -CO- is never substituted.
　なお、炭素数１～２０の炭化水素基中の－ＣＨ2－が、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わったとき、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わった基の炭素数は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わる前の炭化水素基中の炭素数を意味することとする。例えば、＊－Ｏ－ＣＨ2－ＣＨ2－ＣＨ3基は、炭素数４の炭化水素基（＊－ＣＨ2－ＣＨ2－ＣＨ2－ＣＨ3）中の－ＣＨ2－が－Ｏ－に置き換わった基である。
　また、炭素数１～２０の炭化水素基中に置き換わり可能な－ＣＨ2－が複数存在すれば、置き換わりの個数は必ずしも１個に限られない。例えば、炭素数４の炭化水素基（＊－ＣＨ2－ＣＨ2－ＣＨ2－ＣＨ3）中の２個の－ＣＨ2－が－Ｏ－に置き換わって、＊－Ｏ－ＣＨ2－Ｏ－ＣＨ3となることも可能である。すなわち、＊－Ｏ－ＣＨ2－Ｏ－ＣＨ3のように、２個以上の－ＣＨ2－が－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わった基も、「置換基を有していてもよい炭素数１～２０の炭化水素基中の－ＣＨ2－が、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わった基」に含まれる。 When —CH 2 — in a hydrocarbon group having 1 to 20 carbon atoms is replaced with —O—, —S— or —CO—, the group replaced with —O—, —S— or —CO— means the number of carbon atoms in the hydrocarbon group before replacement with -O-, -S- or -CO-. For example, *-O-CH 2 -CH 2 -CH 3 group means that -CH 2 - in a hydrocarbon group having 4 carbon atoms (*-CH 2 -CH 2 -CH 2 -CH 3 ) becomes -O- It is a displaced group.
Further, if a plurality of —CH 2 — substitutable hydrocarbon groups having 1 to 20 carbon atoms exist, the number of substitutions is not necessarily limited to one. For example, two —CH 2 — in a hydrocarbon group having 4 carbon atoms (*—CH 2 —CH 2 —CH 2 —CH 3 ) are replaced with —O— to give *—O—CH 2 —O— It is also possible to be CH3 . That is, groups in which two or more —CH 2 — are replaced with —O—, —S—, or —CO—, such as *—O—CH 2 —O—CH 3 , also have substituents. A group in which -CH 2 - in a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with -O-, -S- or -CO-.
　Ｒa1～Ｒa14、Ｒb1～Ｒb3、Ｒx2、Ｒx4、Ｒx5、Ｒx11、Ｒx12、Ｒx15、Ｒx16、Ｒy1～Ｒy5、Ｒy11、Ｒy12、Ｒy15及びＲy16で表される炭素数１～２０の炭化水素基は置換基を有していてもよい。
　Ｒa1～Ｒa14、Ｒb1～Ｒb3、Ｒx2、Ｒx4、Ｒx5、Ｒx11、Ｒx12、Ｒx15、Ｒx16、Ｒy1～Ｒy5、Ｒy11、Ｒy12、Ｒy15及びＲy16で表される炭素数１～２０の炭化水素基の置換基としては、置換基を有していてもよい複素環基、ハロゲン原子、ニトロ基、シアノ基、－ＯＲxa1、－ＣＯ2Ｒxa1、－ＳＲxa1、－ＳＯ3Ｒxa1、－ＳＯ2ＮＲxa1Ｒxa2及び－ＮＲxa1Ｒxa2等が挙げられる（ただし、Ｒxa1及びＲxa2は前記に同じ）。 R a1 to R a14 , R b1 to R b3 , R x2 , R x4 , R x5 , R x11 , R x12 , R x15 , R x16 , R y1 to R y5 , R y11 , R y12 , R y15 and R y16 The hydrocarbon group having 1 to 20 carbon atoms represented by may have a substituent.
R a1 to R a14 , R b1 to R b3 , R x2 , R x4 , R x5 , R x11 , R x12 , R x15 , R x16 , R y1 to R y5 , R y11 , R y12 , R y15 and R y16 Substituents for the hydrocarbon group having 1 to 20 carbon atoms represented by may be optionally substituted heterocyclic groups, halogen atoms, nitro groups, cyano groups, —OR xa1 , —CO 2 R xa1 , -SR xa1 , -SO 3 R xa1 , -SO 2 NR xa1 R xa2 and -NR xa1 R xa2 (provided that R xa1 and R xa2 are the same as above).
　Ｒa1～Ｒa14、Ｒb1～Ｒb3、Ｒx2、Ｒx4、Ｒx5、Ｒx11、Ｒx12、Ｒx15、Ｒx16、Ｒy1～Ｒy5、Ｒy11、Ｒy12、Ｒy15及びＲy16で表される炭素数１～２０の炭化水素基の置換基として用いられる複素環基は、単環であってもよいし多環であってもよく、好ましくは環の構成要素としてヘテロ原子を含む複素環である。ヘテロ原子としては、窒素原子、酸素原子及び硫黄原子等が挙げられる。
　該複素環としては、Ｒx1及びＲx3で表される炭素数２～２０の脂肪族不飽和炭化水素基の置換基として用いられる複素環基と同じものが例示される。
　該複素環基の炭素数は、好ましくは２～３０であり、より好ましくは３～２２であり、さらに好ましくは３～２０である。
　該複素環基は置換基を有していてもよく、置換基としては、ハロゲン原子、ニトロ基、シアノ基、－ＯＲxa1、－ＣＯ2Ｒxa1、－ＳＲxa1、－ＳＯ3Ｒxa1、－ＳＯ2ＮＲxa1Ｒxa2及び－ＮＲxa1Ｒxa2等が挙げられる（ただし、Ｒxa1及びＲxa2は前記に同じ）。
　なお、該複素環の結合位は、各環に含まれる任意の水素原子が脱離した部分である。 R a1 to R a14 , R b1 to R b3 , R x2 , R x4 , R x5 , R x11 , R x12 , R x15 , R x16 , R y1 to R y5 , R y11 , R y12 , R y15 and R y16 The heterocyclic group used as a substituent of the hydrocarbon group having 1 to 20 carbon atoms represented by may be monocyclic or polycyclic, preferably a heteroatom as a ring constituent is a heterocyclic ring containing Heteroatoms include nitrogen, oxygen and sulfur atoms.
Examples of the heterocyclic ring include the same heterocyclic groups used as substituents of aliphatic unsaturated hydrocarbon groups having 2 to 20 carbon atoms represented by R x1 and R x3 .
The heterocyclic group preferably has 2 to 30 carbon atoms, more preferably 3 to 22 carbon atoms, and still more preferably 3 to 20 carbon atoms.
The heterocyclic group may have a substituent, and examples of the substituent include a halogen atom, a nitro group, a cyano group, —OR xa1 , —CO 2 R xa1 , —SR xa1 , —SO 3 R xa1 , — SO 2 NR xa1 R xa2 and -NR xa1 R xa2 (provided that R xa1 and R xa2 are the same as above).
In addition, the bonding position of the heterocyclic ring is a portion from which any hydrogen atom contained in each ring is eliminated.
　Ｒa1～Ｒa14、Ｒb1～Ｒb3、Ｒx2、Ｒx4、Ｒx5、Ｒx11、Ｒx12、Ｒx15、Ｒx16、Ｒy1～Ｒy5、Ｒy11、Ｒy12、Ｒy15及びＲy16で表される炭素数１～２０の炭化水素基の置換基として用いられるハロゲン原子は、フッ素原子、塩素原子、臭素原子及びヨウ素原子等が例示される。 R a1 to R a14 , R b1 to R b3 , R x2 , R x4 , R x5 , R x11 , R x12 , R x15 , R x16 , R y1 to R y5 , R y11 , R y12 , R y15 and R y16 The halogen atom used as a substituent of the hydrocarbon group having 1 to 20 carbon atoms represented by is exemplified by a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
　Ｒx10、Ｒx14、Ｒy10及びＸy14で表される炭素数１～２０の飽和炭化水素基としては、Ｒa1～Ｒa14、Ｒb1～Ｒb3、Ｒx2、Ｒx4、Ｒx5、Ｒx11～Ｒx13、Ｒx15～Ｒx17、Ｒy1～Ｒy5、Ｒy11～Ｒy13及びＲy15～Ｒy17で表される炭化水素基のうち、直鎖状アルキル基、分枝鎖状アルキル基、シクロアルキル基、及び飽和多環式炭化水素基として例示した基が挙げられる。 The saturated hydrocarbon groups having 1 to 20 carbon atoms represented by R x10 , R x14 , R y10 and X y14 include R a1 to R a14 , R b1 to R b3 , R x2 , R x4 , R x5 , R Of the hydrocarbon groups represented by x11 to R x13 , R x15 to R x17 , R y1 to R y5 , R y11 to R y13 and R y15 to R y17 , straight-chain alkyl groups and branched-chain alkyl groups , the cycloalkyl group, and the groups exemplified as the saturated polycyclic hydrocarbon group.
　Ｒa1～Ｒa14で表される炭素数１～２０の複素環基は、単環であってもよいし多環であってもよく、好ましくは環の構成要素としてヘテロ原子を含む複素環である。ヘテロ原子としては、窒素原子、酸素原子及び硫黄原子等が挙げられる。
　該複素環としては、Ｒx1及びＲx3で表される炭素数２～２０の脂肪族不飽和炭化水素基の置換基として用いられる複素環基と同じものが例示される。
　該複素環基の炭素数は、好ましくは３～２０である。
　該複素環基は置換基を有していてもよく、置換基としては、ハロゲン原子、ニトロ基、シアノ基、炭素数１～１０のアルキル基、－ＯＲxa1、－ＣＯ2Ｒxa1、－ＳＲxa1、－ＳＯ3Ｒxa1、－ＳＯ2ＮＲxa1Ｒxa2及び－ＮＲxa1Ｒxa2等が挙げられる（ただし、Ｒxa1及びＲxa2は前記に同じ）。
　なお、該複素環の結合位は、各環に含まれる任意の水素原子が脱離した部分である。 The heterocyclic group having 1 to 20 carbon atoms represented by R a1 to R a14 may be monocyclic or polycyclic, and is preferably a heterocyclic ring containing a heteroatom as a ring constituent. be. Heteroatoms include nitrogen, oxygen and sulfur atoms.
Examples of the heterocyclic ring include the same heterocyclic groups used as substituents of aliphatic unsaturated hydrocarbon groups having 2 to 20 carbon atoms represented by R x1 and R x3 .
The heterocyclic group preferably has 3 to 20 carbon atoms.
The heterocyclic group may have a substituent, and examples of the substituent include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 10 carbon atoms, —OR xa1 , —CO 2 R xa1 and —SR. xa1 , -SO 3 R xa1 , -SO 2 NR xa1 R xa2 and -NR xa1 R xa2 (provided that R xa1 and R xa2 are the same as above).
In addition, the bonding position of the heterocyclic ring is a portion from which any hydrogen atom contained in each ring is eliminated.
　Ｒx2がＺx2とＲx1とを結ぶ単結合であるとき、Ｒx1の一部又は全部が＊－Ｚx2－Ｐ（＝Ｏ）－Ｚx1－＊（＊は結合手を表す）と一緒になって環が形成される。すなわち、Ｒx2がＺx2とＲx1とを結ぶ単結合であるとき、Ｒx1で表される置換基を有していてもよい炭素数２～２０の脂肪族不飽和炭化水素基中の任意の炭素原子又は置換基を有していてもよい炭素数６～２０の芳香族炭化水素基の任意の炭素原子（好ましくは置換基を有していてもよい炭素数２～２０の脂肪族不飽和炭化水素基中の任意の炭素原子）とＺx2との間で、一対の電子が共有されてできる結合がＲx2で表される単結合に相当する。 when R x2 is a single bond connecting Z x2 and R x1 , part or all of R x1 is combined with *-Z x2 -P(=O)-Z x1 -* (* represents a bond); to form a ring. That is, when R x2 is a single bond connecting Z x2 and R x1 , any of the optionally substituted aliphatic unsaturated hydrocarbon groups having 2 to 20 carbon atoms represented by R x1 or any carbon atom of an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent (preferably an aliphatic hydrocarbon group having 2 to 20 carbon atoms which may have a substituent A bond formed by sharing a pair of electrons between (an arbitrary carbon atom in a saturated hydrocarbon group) and Z x2 corresponds to a single bond represented by R x2 .
　Ｒx1が置換基を有していてもよい炭素数２～２０の脂肪族不飽和炭化水素基である場合、Ｒx1の一部又は全部が＊－Ｚx2－Ｐ（＝Ｏ）－Ｚx1－＊（＊は結合手を表す）と一緒になって形成される環において、該環の構成員となる炭素原子間で不飽和結合が形成されていてもよく、該環の構成員となる炭素原子と該環の構成員外である炭素原子との間で不飽和結合が形成されてもよく、該環の構成員外である炭素原子間で不飽和結合が形成されてもよい。 When R x1 is an optionally substituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms, part or all of R x1 is *-Z x2 -P(=O)-Z x1 In the ring formed together with -* (* represents a bond), an unsaturated bond may be formed between the carbon atoms that are members of the ring, and is a member of the ring An unsaturated bond may be formed between a carbon atom and a carbon atom that is not a member of the ring, and an unsaturated bond may be formed between carbon atoms that are not a member of the ring.
　またＲy2がＺy3とＲy1とを結ぶ単結合であるとき、Ｒy1は置換基を有していてもよい炭素数１～２０の炭化水素基であり、Ｒy1の一部又は全部が＊－Ｚy3－Ｐ（＝Ｚy1）－Ｚy2－＊（＊は結合手を表す）と一緒になって環が形成される。すなわち、Ｒy2がＺy3とＲy1とを結ぶ単結合であるとき、Ｒy1で表される置換基を有していてもよい炭素数１～２０の炭化水素基中の任意の炭素原子とＺy3との間で、一対の電子が共有されてできる結合がＲy2で表される単結合に相当する。 Further, when R y2 is a single bond connecting Z y3 and R y1 , R y1 is an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and part or all of R y1 is Together with *-Z y3 -P(=Z y1 )-Z y2 -* (* represents a bond), a ring is formed. That is, when R y2 is a single bond connecting Z y3 and R y1 , any carbon atom in the optionally substituted hydrocarbon group having 1 to 20 carbon atoms represented by R y1 A bond formed by sharing a pair of electrons with Z y3 corresponds to a single bond represented by R y2 .
　ｎｘ１～ｎｘ１２及びｎｙ１～ｎｙ１２は、それぞれ独立に、０～４の整数を表す。ｎｘ１～ｎｘ４は、同一であっても異なっていてもよいが、同一であることが好ましく、ｎｘ５～ｎｘ１２は、同一であっても異なっていてもよいが、同一であることが好ましく、ｎｙ１～ｎｙ４は、同一であっても異なっていてもよいが、同一であることが好ましく、ｎｙ５～ｎｙ１２は、同一であっても異なっていてもよいが、同一であることが好ましい。ｎｘ１が２以上の整数を表す場合、複数のＸx1は同一であっても異なっていてもよい。ｎｘ２～ｎｘ１２及びｎｙ１～ｎｙ１２が２以上の整数を表す場合の複数のＸx2～Ｘx12及びＸy1～Ｘy12についても同様である。 nx1 to nx12 and ny1 to ny12 each independently represent an integer of 0 to 4; nx1 to nx4 may be the same or different, but are preferably the same; nx5 to nx12 may be the same or different, but are preferably the same; ny4 may be the same or different but is preferably the same, and ny5 to ny12 may be the same or different but are preferably the same. When nx1 represents an integer of 2 or more, multiple X x1 may be the same or different. The same applies to a plurality of X x2 to X x12 and X y1 to X y12 when nx2 to nx12 and ny1 to ny12 represent integers of 2 or more.
　Ｘx1の置換位置は特段限定されないが、ｎｘ１が１の場合、下記部分構造式における２位又は３位の位置であることが好ましく、ｎｘ１が２の場合、下記構造式における２位及び３位の位置であることが好ましい。Ｘx2～Ｘx12及びＸy1～Ｘy12の置換位置についても同様である。なお下記部分構造式において、＊は結合手を示す。 The substitution position of X x1 is not particularly limited, but when nx1 is 1, it is preferably at the 2nd or 3rd position in the following partial structural formula, position is preferred. The same applies to the substitution positions of X x2 to X x12 and X y1 to X y12 . In the partial structural formula below, * indicates a bond.
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
　Ｘx1～Ｘx12及びＸy1～Ｘy12で表されるハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子等が挙げられ、フッ素原子、塩素原子、又は臭素原子であることが好ましく、フッ素原子がより好ましい。 Halogen atoms represented by X x1 to X x12 and X y1 to X y12 include fluorine, chlorine, bromine and iodine atoms, preferably fluorine, chlorine or bromine. , more preferably a fluorine atom.
　Ｘx1～Ｘx4で表される－Ｒx4、Ｘx5～Ｘx12で表される－Ｒx5、Ｘy1～Ｘy4で表される－Ｒy4又はＸy5～Ｘy12で表される－Ｒy5は、炭素数１～２０の脂肪族炭化水素基が好ましく、炭素数１～２０の飽和鎖状炭化水素基がより好ましく、炭素数１～１０の飽和鎖状炭化水素基がさらに好ましく、炭素数１～５の分枝鎖状アルキル基がよりさらに好ましく、ｔｅｒｔ－ブチル基が特に好ましい。 -R x4 represented by X x1 to X x4 , -R x5 represented by X x5 to X x12 , -R y4 represented by X y1 to X y4 or -R represented by X y5 to X y12 y5 is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably a saturated chain hydrocarbon group having 1 to 20 carbon atoms, still more preferably a saturated chain hydrocarbon group having 1 to 10 carbon atoms, A branched alkyl group having a number of 1 to 5 is more preferred, and a tert-butyl group is particularly preferred.
　ＲX13、ＲX17、Ｒy13及びＲy17としては、それぞれ独立に、水素原子又は炭素数１～２０の飽和鎖状炭化水素基が好ましく、水素原子又は炭素数１～１０の飽和鎖状炭化水素基がより好ましく、水素原子又は炭素数１～５の飽和鎖状炭化水素基がさらに好ましい。 R X13 , R X17 , R y13 and R y17 are each independently preferably a hydrogen atom or a saturated chain hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom or a saturated chain hydrocarbon group having 1 to 10 carbon atoms. is more preferred, and a hydrogen atom or a saturated chain hydrocarbon group having 1 to 5 carbon atoms is even more preferred.
　Ｔ+、Ｑ+、Ｍ+、Ｗ+で表されるアルカリ金属イオンとしては、それぞれ独立に、リチウムイオン、ナトリウムイオン、又はカリウムイオンが好ましい。 Alkali metal ions represented by T + , Q + , M + , and W + are each independently preferably lithium ion, sodium ion, or potassium ion.
　Ｒx10、Ｒx14、Ｒy10及びＲy14で表される炭素数１～２０の飽和炭化水素基としては、炭素数１～２０の直鎖状又は分枝鎖状アルキル基が好ましく、炭素数１～１０の直鎖状アルキル基がより好ましい。 The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R x10 , R x14 , R y10 and R y14 is preferably a linear or branched alkyl group having 1 to 20 carbon atoms. ~10 linear alkyl groups are more preferred.
　ＲX11、ＲX12、ＲX15、ＲX16、Ｒy11、Ｒy12、Ｒy15及びＲy16としては、それぞれ独立に、水素原子又は炭素数１～２０の飽和鎖状炭化水素基が好ましく、水素原子又は炭素数１～１０の飽和鎖状炭化水素基がより好ましく、水素原子又は炭素数１～５の飽和鎖状炭化水素基がさらに好ましい。 R x11 , R x12 , R x15 , R x16 , R y11 , R y12 , R y15 and R y16 are each independently preferably a hydrogen atom or a saturated chain hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom Alternatively, a saturated chain hydrocarbon group having 1 to 10 carbon atoms is more preferable, and a hydrogen atom or a saturated chain hydrocarbon group having 1 to 5 carbon atoms is more preferable.
　式（ＸＩ）において、
　Ｒx1は、
　置換基を有していてもよい炭素数２～２０の不飽和鎖状炭化水素基又は置換基を有していてもよい炭素数６～１０の芳香族炭化水素基が好ましく、
　置換基を有していてもよい炭素数２～１０の不飽和鎖状炭化水素基又は置換基を有していてもよい炭素数６～８の芳香族炭化水素基がより好ましく、
　置換基を有していてもよい炭素数２～７の不飽和鎖状炭化水素基又は置換基を有していてもよい炭素数６～７の芳香族炭化水素基がさらに好ましく、
　置換基を有していてもよいエテニル基、置換基を有していてもよいプロペニル基、置換基を有していてもよいブテニル基、置換基を有していてもよい３－メチル－２－ブテニル基、置換基を有していてもよい３－メチル－１，２－ブタジエニル基、置換基を有していてもよいヘプテニル基、置換基を有していてもよいエチニル基、置換基を有していてもよいプロピニル基、置換基を有していてもよいブチニル基、又は置換基を有していてもよいフェニル基が特に好ましい。
　Ｒx1で表される炭素数２～２０の脂肪族不飽和炭化水素基が置換基を有する場合、該置換基としてはフェニル基が好ましい。
　Ｒx2は、
　置換基を有していてもよい炭素数６～２０の芳香族炭化水素基又は置換基を有していてもよい炭素数２～２０の脂肪族不飽和炭化水素基が好ましい。ここで、前記炭素数２～２０の脂肪族不飽和炭化水素基としては、前述のアルケニル基、アルキニル基、不飽和脂環式炭化水素基として説明した基が挙げられる。前記炭素数２～２０の脂肪族不飽和炭化水素基が有していてもよい置換基としては、Ｒx1及びＲx3で表される炭素数２～２０の脂肪族不飽和炭化水素基が有していてもよい置換基として説明した基が挙げられる。ただし、前記脂肪族不飽和炭化水素基が置換基として芳香族炭化水素基を有する場合、脂肪族不飽和炭化水素基の炭素数と置換基としての芳香族炭化水素基の炭素数の合計は２０以下である。置換基として芳香族炭化水素基を有する脂肪族不飽和炭化水素基としては、例えば、アリールアルケニル基、アリールアルキニル基として例示した基が具体的に挙げられる。
　中でもＲx2は、
　置換基を有していてもよい炭素数６～１０の芳香族炭化水素基又は置換基を有していてもよい炭素数２～２０の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）がより好ましく、
　置換基を有していてもよい炭素数６～８の芳香族炭化水素基又は置換基を有していてもよい炭素数２～７の不飽和鎖状炭化水素基がさらに好ましく、
　置換基を有していてもよいフェニル基、置換基を有していてもよいエテニル基、置換基を有していてもよいプロペニル基、置換基を有していてもよいブテニル基、置換基を有していてもよい３－メチル－２－ブテニル基、置換基を有していてもよい３－メチル－１，２－ブタジエニル基、置換基を有していてもよいヘプテニル基、置換基を有していてもよいエチニル基、置換基を有していてもよいプロピニル基、又は置換基を有していてもよいブチニル基が特に好ましい。
　Ｒx2で表される炭素数２～２０の脂肪族不飽和炭化水素基が置換基を有する場合、該置換基としては炭素数６～１０の芳香族炭化水素基が好ましく、フェニル基がより好ましい。 In formula (XI),
R x1 is
An optionally substituted unsaturated chain hydrocarbon group having 2 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms is preferred,
An optionally substituted unsaturated chain hydrocarbon group having 2 to 10 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 8 carbon atoms is more preferable,
An optionally substituted unsaturated chain hydrocarbon group having 2 to 7 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 7 carbon atoms is more preferable,
optionally substituted ethenyl group, optionally substituted propenyl group, optionally substituted butenyl group, optionally substituted 3-methyl-2 -butenyl group, optionally substituted 3-methyl-1,2-butadienyl group, optionally substituted heptenyl group, optionally substituted ethynyl group, substituent A propynyl group optionally having , a butynyl group optionally having a substituent, or a phenyl group optionally having a substituent are particularly preferable.
When the aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms represented by R x1 has a substituent, the substituent is preferably a phenyl group.
Rx2 is
An optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms or an optionally substituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms is preferred. Here, examples of the aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms include the groups described above as the alkenyl group, alkynyl group and unsaturated alicyclic hydrocarbon group. Examples of substituents that the C2-C20 aliphatic unsaturated hydrocarbon group may have include C2-C20 aliphatic unsaturated hydrocarbon groups represented by R x1 and R x3 . The groups described as the optional substituents can be mentioned. However, when the aliphatic unsaturated hydrocarbon group has an aromatic hydrocarbon group as a substituent, the total carbon number of the aliphatic unsaturated hydrocarbon group and the aromatic hydrocarbon group as a substituent is 20. It is below. Specific examples of the aliphatic unsaturated hydrocarbon group having an aromatic hydrocarbon group as a substituent include groups exemplified as arylalkenyl groups and arylalkynyl groups.
Among them, R x2 is
An optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms or an unsaturated chain hydrocarbon group having 2 to 20 carbon atoms which may have a substituent (i.e. alkenyl group, alkynyl group) is more preferred,
An optionally substituted aromatic hydrocarbon group having 6 to 8 carbon atoms or an optionally substituted unsaturated chain hydrocarbon group having 2 to 7 carbon atoms is more preferable,
phenyl group optionally having substituent(s), ethenyl group optionally having substituent(s), propenyl group optionally having substituent(s), butenyl group optionally having substituent(s), substituent 3-methyl-2-butenyl group optionally having a substituent, 3-methyl-1,2-butadienyl group optionally having a substituent, a heptenyl group optionally having a substituent, a substituent An optionally substituted ethynyl group, an optionally substituted propynyl group, or an optionally substituted butynyl group is particularly preferred.
When the aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms represented by R x2 has a substituent, the substituent is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, more preferably a phenyl group. .
　式（Ｘ１）、式（Ｘ２）、式（Ｘａ）、式（Ｘ０）及び式（ＸＩ）において、
　Ｘx1～Ｘx4は、それぞれ独立に、－Ｒx4またはハロゲン原子が好ましく、炭素数１～１０の直鎖状又は分枝鎖状のアルキル基、或いはハロゲン原子がより好ましく、炭素数１～５の分枝鎖状アルキル基またはハロゲン原子がさらに好ましく、ｔｅｒｔ－ブチル基、フッ素原子、塩素原子、または臭素原子が特に好ましい。
　ｎｘ１～ｎｘ４は、それぞれ独立に、例えば０～２または４であり、好ましくは０～２、より好ましくは０～１、さらに好ましくは０である。 In formula (X1), formula (X2), formula (Xa), formula (X0) and formula (XI),
X x1 to X x4 are each independently preferably —R x4 or a halogen atom, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, or a halogen atom, and 1 to 5 carbon atoms. is more preferred, and a tert-butyl group, a fluorine atom, a chlorine atom, or a bromine atom is particularly preferred.
nx1 to nx4 are each independently, for example, 0 to 2 or 4, preferably 0 to 2, more preferably 0 to 1, still more preferably 0.
　式（ＸＩＩ）において、
　Ｒx3は、
　置換基を有していてもよい炭素数２～２０の不飽和鎖状炭化水素基又は置換基を有していてもよい炭素数６～１０の芳香族炭化水素基が好ましく、
　置換基を有していてもよい炭素数２～１０の不飽和鎖状炭化水素基又は置換基を有していてもよい炭素数６～８の芳香族炭化水素基がより好ましく、
　置換基を有していてもよい炭素数２～５の不飽和鎖状炭化水素基又は置換基を有していてもよい炭素数６～７の芳香族炭化水素基がさらに好ましく、
　置換基を有していてもよいエテニル基、置換基を有していてもよいプロペニル基、置換基を有していてもよいブテニル基、置換基を有していてもよいエチニル基、置換基を有していてもよいプロピニル基、置換基を有していてもよいブチニル基、又は置換基を有していてもよいフェニル基が特に好ましい。
　Ｒx3で表される炭素数２～２０の脂肪族不飽和炭化水素基が置換基を有する場合、該置換基としては炭素数６～１０の芳香族炭化水素基が好ましく、フェニル基がより好ましい。 In formula (XII),
R x3 is
An optionally substituted unsaturated chain hydrocarbon group having 2 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms is preferred,
An optionally substituted unsaturated chain hydrocarbon group having 2 to 10 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 8 carbon atoms is more preferable,
An optionally substituted unsaturated chain hydrocarbon group having 2 to 5 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 7 carbon atoms is more preferable,
optionally substituted ethenyl group, optionally substituted propenyl group, optionally substituted butenyl group, optionally substituted ethynyl group, substituent A propynyl group optionally having , a butynyl group optionally having a substituent, or a phenyl group optionally having a substituent are particularly preferable.
When the aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms represented by R x3 has a substituent, the substituent is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, more preferably a phenyl group. .
　式（Ｘ３）、式（Ｘｂ）又は式（ＸＩＩ）において、
　Ｘx5～Ｘx12は、それぞれ独立に、－Ｒx5またはハロゲン原子が好ましく、炭素数１～１０の直鎖状又は分枝鎖状のアルキル基、或いはハロゲン原子がより好ましく、炭素数１～５の分枝鎖状アルキル基またはハロゲン原子がさらに好ましく、ｔｅｒｔ－ブチル基、フッ素原子、塩素原子、または臭素原子が特に好ましい。
　ｎｘ５～ｎｘ１２は、それぞれ独立に、例えば０～２または４であり、好ましくは０～２、より好ましくは０～１、さらに好ましくは０である。 In formula (X3), formula (Xb) or formula (XII),
X x5 to X x12 are each independently preferably —R x5 or a halogen atom, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, or a halogen atom, and 1 to 5 carbon atoms. is more preferred, and a tert-butyl group, a fluorine atom, a chlorine atom, or a bromine atom is particularly preferred.
nx5 to nx12 are each independently, for example, 0 to 2 or 4, preferably 0 to 2, more preferably 0 to 1, still more preferably 0.
　本発明の着色剤として含まれるフタロシアニン化合物は、
　式（Ｘ１）で表される化合物、式（Ｘ２）で表される化合物及び式（Ｘ３）で表される化合物からなる群から選択される少なくとも１種であることが好ましく、
　式（Ｘａ）で表される化合物、式（Ｘｂ）で表される化合物、式（ＹＩ）で表される化合物、式（ＹＩＩ）で表される化合物、Ｃ．Ｉ．ピグメントブルー１５、Ｃ．Ｉ．ピグメントブルー１５：１、Ｃ．Ｉ．ピグメントブルー１５：２、Ｃ．Ｉ．ピグメントブルー１５：３、Ｃ．Ｉ．ピグメントブルー１５：４、Ｃ．Ｉ．ピグメントブルー１５：６、Ｃ．Ｉ．ピグメントブルー１６、Ｃ．Ｉ．ピグメントグリーン７、Ｃ．Ｉ．ピグメントグリーン３６、Ｃ．Ｉ．ピグメントグリーン５８、Ｃ．Ｉ．ピグメントグリーン５９、Ｃ．Ｉ．ピグメントグリーン６２、及びＣ．Ｉ．ピグメントグリーン６３からなる群から選択される少なくとも１種であることがより好ましく、
　式（Ｘ０）で表される化合物、式（ＸＩ）で表される化合物、式（ＸＩＩ）で表される化合物、Ｃ．Ｉ．ピグメントブルー１５、Ｃ．Ｉ．ピグメントブルー１５：１、Ｃ．Ｉ．ピグメントブルー１５：２、Ｃ．Ｉ．ピグメントブルー１５：３、Ｃ．Ｉ．ピグメントブルー１５：４、Ｃ．Ｉ．ピグメントブルー１５：６、Ｃ．Ｉ．ピグメントブルー１６、Ｃ．Ｉ．ピグメントグリーン７、Ｃ．Ｉ．ピグメントグリーン３６、Ｃ．Ｉ．ピグメントグリーン５８、Ｃ．Ｉ．ピグメントグリーン５９、Ｃ．Ｉ．ピグメントグリーン６２、及びＣ．Ｉ．ピグメントグリーン６３からなる群から選択される少なくとも１種であることがさらに好ましく、
　式（Ｘ０）で表される化合物、式（ＸＩ）で表される化合物、及び式（ＸＩＩ）で表される化合物からなる群から選択される少なくとも１種であることがよりさらに好ましい。 The phthalocyanine compound contained as the coloring agent of the present invention is
It is preferably at least one selected from the group consisting of a compound represented by formula (X1), a compound represented by formula (X2) and a compound represented by formula (X3),
C. a compound represented by formula (Xa), a compound represented by formula (Xb), a compound represented by formula (YI), a compound represented by formula (YII); I. Pigment Blue 15, C.I. I. Pigment Blue 15:1, C.I. I. Pigment Blue 15:2, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 15:6, C.I. I. Pigment Blue 16, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59, C.I. I. Pigment Green 62, and C.I. I. It is more preferably at least one selected from the group consisting of Pigment Green 63,
C. a compound represented by formula (X0), a compound represented by formula (XI), a compound represented by formula (XII); I. Pigment Blue 15, C.I. I. Pigment Blue 15:1, C.I. I. Pigment Blue 15:2, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 15:6, C.I. I. Pigment Blue 16, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59, C.I. I. Pigment Green 62, and C.I. I. It is more preferably at least one selected from the group consisting of Pigment Green 63,
It is more preferably at least one selected from the group consisting of the compound represented by formula (X0), the compound represented by formula (XI), and the compound represented by formula (XII).
　式（Ｘ０）で表される化合物としては、式（Ｘ０Ａ）～式（Ｘ０Ｅ）で表される化合物が好ましい。 As the compound represented by formula (X0), compounds represented by formulas (X0A) to (X0E) are preferable.
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
　式（ＸＩ）で表される化合物としては、式（ＸＩＡ）～式（ＸＩＥ）で表される化合物が好ましい。 As the compound represented by formula (XI), compounds represented by formulas (XIA) to (XIE) are preferable.
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
［式（ＸＩＡ）～式（ＸＩＥ）中、Ｒx1、Ｒx2、Ｚx1及びＺx2は、前記に同じ。］ [In formulas (XIA) to (XIE), R x1 , R x2 , Z x1 and Z x2 are the same as above. ]
　式（ＸＩＡ）で表される化合物としては、例えば、表１～表４に示す式（ＸＩＡ－１）～式（ＸＩＡ－１９０）で表される化合物が挙げられる。
　式（ＸＩＢ）で表される化合物としては、例えば、表５～表８に示す式（ＸＩＢ－１）～式（ＸＩＢ－１９０）で表される化合物が挙げられる。
　式（ＸＩＣ）で表される化合物としては、例えば、表９～表１２に示す式（ＸＩＣ－１）～式（ＸＩＣ－１９０）で表される化合物が挙げられる。
　式（ＸＩＤ）で表される化合物としては、例えば、表１３～表１６に示す式（ＸＩＤ－１）～式（ＸＩＤ－１９０）で表される化合物が挙げられる。
　式（ＸＩＥ）で表される化合物としては、例えば、表１７～表２０に示す式（ＸＩＥ－１）～式（ＸＩＥ－１９０）で表される化合物が挙げられる。
　なお、表１～表３、表５～表７、表９～表１１、表１３～表１５及び表１７～表１９中の「Ｒx1」欄及び「Ｒx2」欄に記載されている記号は、それぞれ式（ｘｉ－１）～式（ｘｉ－１２）及び式（ｘｉｉ－１）で表される基に対応している。
　また表４、表８、表１２、表１６、及び表２０中の「Ｒx1とＲx2が形成する基」欄に記載されている記号は、それぞれ式（ｘｃａ－１）～式（ｘｃａ－２）、式（ｘｃｂ－１）、式（ｘｃｃ－１）で表される基に対応している。なお、「Ｒx1とＲx2が形成する基」とは、Ｒx2がＺx2とＲx1とを結ぶ単結合であるとき、＊－Ｚx2－Ｐ（＝Ｏ）－Ｚx1－＊（＊は結合手を表す）における結合手＊に結合する基を表す。
　式（ｘｃａ－１）～式（ｘｃａ－２）中、Ｒx6及びＲx7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１～２０の炭化水素基を表し、前記置換基を有していてもよい炭素数１～２０の炭化水素基としては、Ｒb1～Ｒb3、Ｒx2、Ｒx4、Ｒx5及びＲy1～Ｒy5等で表される置換基を有していてもよい炭素数１～２０の炭化水素基と同じものが挙げられる。Ｒx6及びＲx7は、それぞれ独立に、水素原子或いは炭素数１～１０の直鎖状又は分枝鎖状のアルキル基が好ましい。
　＊は、結合手を表す。 Examples of compounds represented by formula (XIA) include compounds represented by formulas (XIA-1) to (XIA-190) shown in Tables 1 to 4.
Examples of compounds represented by formula (XIB) include compounds represented by formulas (XIB-1) to (XIB-190) shown in Tables 5 to 8.
Examples of compounds represented by formula (XIC) include compounds represented by formulas (XIC-1) to (XIC-190) shown in Tables 9 to 12.
Examples of compounds represented by formula (XID) include compounds represented by formulas (XID-1) to (XID-190) shown in Tables 13 to 16.
Examples of compounds represented by formula (XIE) include compounds represented by formulas (XIE-1) to (XIE-190) shown in Tables 17 to 20.
The symbols described in the "R x1 " and "R x2 " columns in Tables 1 to 3, Tables 5 to 7, Tables 9 to 11, Tables 13 to 15, and Tables 17 to 19 correspond to groups represented by formulas (xi-1) to (xi-12) and formula (xii-1), respectively.
In addition, the symbols described in the column "group formed by R x1 and R x2 " in Tables 4, 8, 12, 16 and 20 are represented by formulas (xca-1) to (xca- 2), which corresponds to the groups represented by the formulas (xcb-1) and (xcc-1). The term "group formed by R x1 and R x2 " means *-Z x2 -P(=O)-Z x1 -*(* when R x2 is a single bond connecting Z x2 and R x1 represents a bond) represents a group that binds to the bond *.
In formulas (xca-1) to (xca-2), R x6 and R x7 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, Examples of the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent include substituents represented by R b1 to R b3 , R x2 , R x4 , R x5 and R y1 to R y5 . The same as the hydrocarbon group having 1 to 20 carbon atoms which may be present may be mentioned. R x6 and R x7 are each independently preferably a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms.
* represents a bond.
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000047
Figure JPOXMLDOC01-appb-T000047
Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000049
Figure JPOXMLDOC01-appb-T000049
　式（ＸＩＡ）で表される化合物としては、
　式（ＸＩＡ－１）～式（ＸＩＡ－１２）、式（ＸＩＡ－９１）～式（ＸＩＡ－１０２）、式（ＸＩＡ－１０３）～式（ＸＩＡ－１０８）、式（ＸＩＡ－１１５）～式（ＸＩＡ－１１９）、式（ＸＩＡ－１２６）～式（ＸＩＡ－１２９）、式（ＸＩＡ－１３６）～式（ＸＩＡ－１３８）、式（ＸＩＡ－１４５）～式（ＸＩＡ－１４６）、式（ＸＩＡ－１５３）、式（ＸＩＡ－１８１）～式（ＸＩＡ－１９０）で表される化合物が好ましく、
　式（ＸＩＡ－１）～式（ＸＩＡ－１２）、式（ＸＩＡ－１０３）～式（ＸＩＡ－１０５）、式（ＸＩＡ－１１５）～式（ＸＩＡ－１１６）、式（ＸＩＡ－１２６）、式（ＸＩＡ－１３６）～式（ＸＩＡ－１３８）、式（ＸＩＡ－１４５）～式（ＸＩＡ－１４６）、式（ＸＩＡ－１５３）、式（ＸＩＡ－１８１）～式（ＸＩＡ－１８２）、式（ＸＩＡ－１８３）～式（ＸＩＡ－１８４）、式（ＸＩＡ－１８７）～式（ＸＩＡ－１８８）で表される化合物がより好ましく、
　式（ＸＩＡ－１）、式（ＸＩＡ－１０）、式（ＸＩＡ－１１）、式（ＸＩＡ－１２）、式（ＸＩＡ－１１５）、式（ＸＩＡ－１２６）、式（ＸＩＡ－１４５）、式（ＸＩＡ－１５３）、式（ＸＩＡ－１８１）、式（ＸＩＡ－１８２）、式（ＸＩＡ－１８３）、式（ＸＩＡ－１８４）、式（ＸＩＡ－１８７）で表される化合物がさらに好ましく、
　式（ＸＩＡ－１１５）、式（ＸＩＡ－１２６）、式（ＸＩＡ－１８２）で表される化合物がよりさらに好ましい。 As the compound represented by the formula (XIA),
Formula (XIA-1) ~ Formula (XIA-12), Formula (XIA-91) ~ Formula (XIA-102), Formula (XIA-103) ~ Formula (XIA-108), Formula (XIA-115) ~ Formula (XIA-119), Formula (XIA-126) ~ Formula (XIA-129), Formula (XIA-136) ~ Formula (XIA-138), Formula (XIA-145) ~ Formula (XIA-146), Formula ( XIA-153), compounds represented by formulas (XIA-181) to (XIA-190) are preferred,
Formula (XIA-1) ~ Formula (XIA-12), Formula (XIA-103) ~ Formula (XIA-105), Formula (XIA-115) ~ Formula (XIA-116), Formula (XIA-126), Formula (XIA-136) ~ formula (XIA-138), formula (XIA-145) ~ formula (XIA-146), formula (XIA-153), formula (XIA-181) ~ formula (XIA-182), formula ( XIA-183) ~ formula (XIA-184), more preferably compounds represented by formula (XIA-187) ~ formula (XIA-188),
Formula (XIA-1), Formula (XIA-10), Formula (XIA-11), Formula (XIA-12), Formula (XIA-115), Formula (XIA-126), Formula (XIA-145), Formula Compounds represented by (XIA-153), formula (XIA-181), formula (XIA-182), formula (XIA-183), formula (XIA-184), and formula (XIA-187) are more preferred,
Compounds represented by Formula (XIA-115), Formula (XIA-126), and Formula (XIA-182) are more preferred.
Figure JPOXMLDOC01-appb-T000050
Figure JPOXMLDOC01-appb-T000050
Figure JPOXMLDOC01-appb-T000051
Figure JPOXMLDOC01-appb-T000051
Figure JPOXMLDOC01-appb-T000052
Figure JPOXMLDOC01-appb-T000052
Figure JPOXMLDOC01-appb-T000053
Figure JPOXMLDOC01-appb-T000053
　式（ＸＩＢ）で表される化合物としては、
　式（ＸＩＢ－１）～式（ＸＩＢ－１２）、式（ＸＩＢ－９１）～式（ＸＩＢ－１０２）、式（ＸＩＢ－１０３）～式（ＸＩＢ－１０８）、式（ＸＩＢ－１１５）～式（ＸＩＢ－１１９）、式（ＸＩＢ－１２６）～式（ＸＩＢ－１２９）、式（ＸＩＢ－１３６）～式（ＸＩＢ－１３８）、式（ＸＩＢ－１４５）～式（ＸＩＢ－１４６）、式（ＸＩＢ－１５３）、式（ＸＩＢ－１８１）～式（ＸＩＢ－１９０）で表される化合物が好ましく、
　式（ＸＩＢ－１）～式（ＸＩＢ－１２）で表される化合物がより好ましく、
　式（ＸＩＢ－１）で表される化合物がさらに好ましい。 As the compound represented by the formula (XIB),
Formula (XIB-1) ~ Formula (XIB-12), Formula (XIB-91) ~ Formula (XIB-102), Formula (XIB-103) ~ Formula (XIB-108), Formula (XIB-115) ~ Formula (XIB-119), Formula (XIB-126) ~ Formula (XIB-129), Formula (XIB-136) ~ Formula (XIB-138), Formula (XIB-145) ~ Formula (XIB-146), Formula ( XIB-153), compounds represented by formulas (XIB-181) to (XIB-190) are preferred,
Compounds represented by formulas (XIB-1) to (XIB-12) are more preferred,
Compounds represented by formula (XIB-1) are more preferred.
Figure JPOXMLDOC01-appb-T000054
Figure JPOXMLDOC01-appb-T000054
Figure JPOXMLDOC01-appb-T000055
Figure JPOXMLDOC01-appb-T000055
Figure JPOXMLDOC01-appb-T000056
Figure JPOXMLDOC01-appb-T000056
Figure JPOXMLDOC01-appb-T000057
Figure JPOXMLDOC01-appb-T000057
　式（ＸＩＣ）で表される化合物としては、
　式（ＸＩＣ－１）～式（ＸＩＣ－１２）、式（ＸＩＣ－９１）～式（ＸＩＣ－１０２）、式（ＸＩＣ－１０３）～式（ＸＩＣ－１０８）、式（ＸＩＣ－１１５）～式（ＸＩＣ－１１９）、式（ＸＩＣ－１２６）～式（ＸＩＣ－１２９）、式（ＸＩＣ－１３６）～式（ＸＩＣ－１３８）、式（ＸＩＣ－１４５）～式（ＸＩＣ－１４６）、式（ＸＩＣ－１５３）、式（ＸＩＣ－１８１）～式（ＸＩＣ－１９０）で表される化合物が好ましく、
　式（ＸＩＣ－１）～式（ＸＩＣ－１２）、式（ＸＩＣ－１０３）～式（ＸＩＣ－１０５）、式（ＸＩＣ－１１５）～式（ＸＩＣ－１１６）、式（ＸＩＣ－１２６）で表される化合物がより好ましく、
　式（ＸＩＣ－１）、式（ＸＩＣ－１１５）で表される化合物がさらに好ましい。 As the compound represented by the formula (XIC),
Formula (XIC-1) ~ Formula (XIC-12), Formula (XIC-91) ~ Formula (XIC-102), Formula (XIC-103) ~ Formula (XIC-108), Formula (XIC-115) ~ Formula (XIC-119), Formula (XIC-126) ~ Formula (XIC-129), Formula (XIC-136) ~ Formula (XIC-138), Formula (XIC-145) ~ Formula (XIC-146), Formula ( XIC-153), compounds represented by formulas (XIC-181) to (XIC-190) are preferred,
Formula (XIC-1) ~ Formula (XIC-12), Formula (XIC-103) ~ Formula (XIC-105), Formula (XIC-115) ~ Formula (XIC-116), Formula (XIC-126) is more preferred,
Compounds represented by formula (XIC-1) and formula (XIC-115) are more preferred.
Figure JPOXMLDOC01-appb-T000058
Figure JPOXMLDOC01-appb-T000058
Figure JPOXMLDOC01-appb-T000059
Figure JPOXMLDOC01-appb-T000059
Figure JPOXMLDOC01-appb-T000060
Figure JPOXMLDOC01-appb-T000060
Figure JPOXMLDOC01-appb-T000061
Figure JPOXMLDOC01-appb-T000061
　式（ＸＩＤ）で表される化合物としては、
　式（ＸＩＤ－１）～式（ＸＩＤ－１２）、式（ＸＩＤ－９１）～式（ＸＩＤ－１０２）、式（ＸＩＤ－１０３）～式（ＸＩＤ－１０８）、式（ＸＩＤ－１１５）～式（ＸＩＤ－１１９）、式（ＸＩＤ－１２６）～式（ＸＩＤ－１２９）、式（ＸＩＤ－１３６）～式（ＸＩＤ－１３８）、式（ＸＩＤ－１４５）～式（ＸＩＤ－１４６）、式（ＸＩＤ－１５３）、式（ＸＩＤ－１８１）～式（ＸＩＤ－１９０）で表される化合物が好ましく、
　式（ＸＩＤ－１）～式（ＸＩＤ－１２）で表される化合物がより好ましく、
　式（ＸＩＤ－１）で表される化合物がさらに好ましい。 As the compound represented by the formula (XID),
Formula (XID-1) ~ Formula (XID-12), Formula (XID-91) ~ Formula (XID-102), Formula (XID-103) ~ Formula (XID-108), Formula (XID-115) ~ Formula (XID-119), Formula (XID-126) ~ Formula (XID-129), Formula (XID-136) ~ Formula (XID-138), Formula (XID-145) ~ Formula (XID-146), Formula ( XID-153), compounds represented by formulas (XID-181) to (XID-190) are preferred,
Compounds represented by formulas (XID-1) to (XID-12) are more preferred,
Compounds represented by formula (XID-1) are more preferred.
Figure JPOXMLDOC01-appb-T000062
Figure JPOXMLDOC01-appb-T000062
Figure JPOXMLDOC01-appb-T000063
Figure JPOXMLDOC01-appb-T000063
Figure JPOXMLDOC01-appb-T000064
Figure JPOXMLDOC01-appb-T000064
Figure JPOXMLDOC01-appb-T000065
Figure JPOXMLDOC01-appb-T000065
　式（ＸＩＥ）で表される化合物としては、
　式（ＸＩＥ－１）～式（ＸＩＥ－１２）、式（ＸＩＥ－９１）～式（ＸＩＥ－１０２）、式（ＸＩＥ－１０３）～式（ＸＩＥ－１０８）、式（ＸＩＥ－１１５）～式（ＸＩＥ－１１９）、式（ＸＩＥ－１２６）～式（ＸＩＥ－１２９）、式（ＸＩＥ－１３６）～式（ＸＩＥ－１３８）、式（ＸＩＥ－１４５）～式（ＸＩＥ－１４６）、式（ＸＩＥ－１５３）、式（ＸＩＥ－１８１）～式（ＸＩＥ－１９０）で表される化合物が好ましく、
　式（ＸＩＥ－１）～式（ＸＩＥ－１２）、式（ＸＩＥ－１０３）～式（ＸＩＥ－１０５）、式（ＸＩＥ－１１５）～式（ＸＩＥ－１１６）、式（ＸＩＥ－１２６）で表される化合物がより好ましく、
　式（ＸＩＥ－１）、式（ＸＩＥ－１１５）で表される化合物がさらに好ましい。 As the compound represented by the formula (XIE),
Formula (XIE-1) ~ Formula (XIE-12), Formula (XIE-91) ~ Formula (XIE-102), Formula (XIE-103) ~ Formula (XIE-108), Formula (XIE-115) ~ Formula (XIE-119), Formula (XIE-126) ~ Formula (XIE-129), Formula (XIE-136) ~ Formula (XIE-138), Formula (XIE-145) ~ Formula (XIE-146), Formula ( XIE-153), compounds represented by formulas (XIE-181) to (XIE-190) are preferred,
Formula (XIE-1) ~ Formula (XIE-12), Formula (XIE-103) ~ Formula (XIE-105), Formula (XIE-115) ~ Formula (XIE-116), Formula (XIE-126) is more preferred,
Compounds represented by formula (XIE-1) and formula (XIE-115) are more preferred.
　式（ＸＩＩ）で表される化合物としては、式（ＸＩＩＡ）～式（ＸＩＩＥ）で表される化合物が好ましい。 As the compound represented by formula (XII), compounds represented by formulas (XIIA) to (XIIE) are preferable.
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000067
Figure JPOXMLDOC01-appb-C000067
Figure JPOXMLDOC01-appb-C000068
Figure JPOXMLDOC01-appb-C000068
Figure JPOXMLDOC01-appb-C000069
Figure JPOXMLDOC01-appb-C000069
Figure JPOXMLDOC01-appb-C000070
Figure JPOXMLDOC01-appb-C000070
［式（ＸＩＩＡ）～式（ＸＩＩＥ）中、Ｒx3及びＺx3は、前記に同じ。］ [In formulas (XIIA) to (XIIE), R x3 and Z x3 are the same as above. ]
　式（ＸＩＩＡ）で表される化合物としては、例えば、表２１に示す式（ＸＩＩＡ－１）～式（ＸＩＩＡ－１８）で表される化合物が挙げられる。
　式（ＸＩＩＢ）で表される化合物としては、例えば、表２２に示す式（ＸＩＩＢ－１）～式（ＸＩＩＢ－１８）で表される化合物が挙げられる。
　式（ＸＩＩＣ）で表される化合物としては、例えば、表２３に示す式（ＸＩＩＣ－１）～式（ＸＩＩＣ－１８）で表される化合物が挙げられる。
　式（ＸＩＩＤ）で表される化合物としては、例えば、表２４に示す式（ＸＩＩＤ－１）～式（ＸＩＩＤ－１８）で表される化合物が挙げられる。
　式（ＸＩＩＥ）で表される化合物としては、例えば、表２５に示す式（ＸＩＩＥ－１）～式（ＸＩＩＥ－１８）で表される化合物が挙げられる。
　なお、表２１～表２５中の「Ｒx3」欄に記載されている記号は、式（ｘｉｉｉ－１）～式（ｘｉｉｉ－９）で表される基に対応している。
　＊は、結合手を表す。 Examples of compounds represented by formula (XIIA) include compounds represented by formulas (XIIA-1) to (XIIA-18) shown in Table 21.
Examples of compounds represented by formula (XIIB) include compounds represented by formulas (XIIB-1) to (XIIB-18) shown in Table 22.
Examples of compounds represented by formula (XIIC) include compounds represented by formulas (XIIC-1) to (XIIC-18) shown in Table 23.
Examples of compounds represented by formula (XIID) include compounds represented by formulas (XIID-1) to (XIID-18) shown in Table 24.
Examples of compounds represented by formula (XIIE) include compounds represented by formulas (XIIE-1) to (XIIE-18) shown in Table 25.
The symbols described in the “R x3 ” columns in Tables 21 to 25 correspond to groups represented by formulas (xiii-1) to (xiii-9).
* represents a bond.
Figure JPOXMLDOC01-appb-C000071
Figure JPOXMLDOC01-appb-C000071
Figure JPOXMLDOC01-appb-T000072
Figure JPOXMLDOC01-appb-T000072
　式（ＸＩＩＡ）で表される化合物としては、
　式（ＸＩＩＡ－１）～式（ＸＩＩＡ－６）、式（ＸＩＩＡ－１０）～式（ＸＩＩＡ－１５）で表される化合物が好ましい。 As the compound represented by formula (XIIA),
Compounds represented by formulas (XIIA-1) to (XIIA-6) and formulas (XIIA-10) to (XIIA-15) are preferred.
Figure JPOXMLDOC01-appb-T000073
Figure JPOXMLDOC01-appb-T000073
　式（ＸＩＩＢ）で表される化合物としては、
　式（ＸＩＩＢ－１）～式（ＸＩＩＢ－６）、式（ＸＩＩＢ－１０）～式（ＸＩＩＢ－１５）で表される化合物が好ましい。 As the compound represented by formula (XIIB),
Compounds represented by formulas (XIIB-1) to (XIIB-6) and formulas (XIIB-10) to (XIIB-15) are preferred.
Figure JPOXMLDOC01-appb-T000074
Figure JPOXMLDOC01-appb-T000074
　式（ＸＩＩＣ）で表される化合物としては、
　式（ＸＩＩＣ－１）～式（ＸＩＩＣ－６）、式（ＸＩＩＣ－１０）～式（ＸＩＩＣ－１５）で表される化合物が好ましい。 As the compound represented by formula (XIIC),
Compounds represented by formulas (XIIC-1) to (XIIC-6) and formulas (XIIC-10) to (XIIC-15) are preferred.
Figure JPOXMLDOC01-appb-T000075
Figure JPOXMLDOC01-appb-T000075
　式（ＸＩＩＤ）で表される化合物としては、
　式（ＸＩＩＤ－１）～式（ＸＩＩＤ－６）、式（ＸＩＩＤ－１０）～式（ＸＩＩＤ－１５）で表される化合物が好ましい。 As the compound represented by the formula (XIID),
Compounds represented by formulas (XIID-1) to (XIID-6) and formulas (XIID-10) to (XIID-15) are preferred.
Figure JPOXMLDOC01-appb-T000076
Figure JPOXMLDOC01-appb-T000076
　式（ＸＩＩＥ）で表される化合物としては、
　式（ＸＩＩＥ－１）～式（ＸＩＩＥ－６）、式（ＸＩＩＥ－１０）～式（ＸＩＩＥ－１５）で表される化合物が好ましい。 As the compound represented by the formula (XIIE),
Compounds represented by formulas (XIIE-1) to (XIIE-6) and formulas (XIIE-10) to (XIIE-15) are preferred.
　式（Ｘ０）で表される化合物は、例えば、式（ＸＩＩＩ）で表される化合物と濃硫酸を適宜反応させることにより製造できる。
　式（ＸＩ）で表される化合物は、例えば、式（ＸＩＩＩ）で表される化合物と、式（ＸＩＶ）で表される化合物を適宜反応させることにより製造できる。
　また式（ＸＩＩ）で表される化合物は、例えば、式（ＸＩＩＩａ）で表される化合物と、式（ＸＩＩＩｂ）で表される化合物と、式（ＸＶ）で表される化合物を適宜反応させることにより製造できる。 The compound represented by formula (X0) can be produced, for example, by appropriately reacting the compound represented by formula (XIII) with concentrated sulfuric acid.
A compound represented by formula (XI) can be produced, for example, by appropriately reacting a compound represented by formula (XIII) with a compound represented by formula (XIV).
In addition, the compound represented by formula (XII) can be obtained, for example, by appropriately reacting a compound represented by formula (XIIIa), a compound represented by formula (XIIIb), and a compound represented by formula (XV). can be manufactured by
Figure JPOXMLDOC01-appb-C000077
Figure JPOXMLDOC01-appb-C000077
［式（ＸＩ）、式（ＸＩＩＩ）及び式（ＸＩＶ）中、Ｒx1、Ｒx2、Ｚx1、Ｚx2、Ｘx1～Ｘx4、及びｎｘ１～ｎｘ４は、前記に同じ。］ [In formula (XI), formula (XIII) and formula (XIV), R x1 , R x2 , Z x1 , Z x2 , X x1 to X x4 and nx1 to nx4 are the same as above. ]
Figure JPOXMLDOC01-appb-C000078
Figure JPOXMLDOC01-appb-C000078
［式（ＸＩＩ）、式（ＸＩＩＩａ）、式（ＸＩＩＩｂ）及び式（ＸＶ）中、Ｒx3、Ｚx3、Ｘx7～Ｘx12、及びｎｘ７～ｎｘ１２は、前記に同じ。］ [In formula (XII), formula (XIIIa), formula (XIIIb) and formula (XV), R x3 , Z x3 , X x7 to X x12 and nx7 to nx12 are the same as above. ]
　式（ＹＩ）において、
　Ｒy1は、
　置換基を有していてもよい炭素数６～２０の芳香族炭化水素基が好ましく、
　置換基を有していてもよい炭素数６～１０の芳香族炭化水素基がより好ましく、
　置換基を有していてもよい炭素数６～８の芳香族炭化水素基がさらに好ましく、
　置換基を有していてもよいフェニル基が特に好ましい。
　Ｒy2は、
　置換基を有していてもよい炭素数２～２０の脂肪族不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の芳香族炭化水素基が好ましい。ここで、Ｒy2及び後述のＲy3の好ましい態様における炭素数２～２０の脂肪族不飽和炭化水素基としては、前述のアルケニル基、アルキニル基、不飽和脂環式炭化水素基として説明した基が挙げられる。前記炭素数２～２０の脂肪族不飽和炭化水素基が有していてもよい置換基としては、Ｒx1及びＲx3で表される炭素数２～２０の脂肪族不飽和炭化水素基が有していてもよい置換基として説明した基が挙げられる。ただし、前記脂肪族不飽和炭化水素基が置換基として芳香族炭化水素基を有する場合、脂肪族不飽和炭化水素基の炭素数と置換基としての芳香族炭化水素基の炭素数の合計は２０以下である。置換基として芳香族炭化水素基を有する脂肪族不飽和炭化水素基としては、例えば、アリールアルケニル基、アリールアルキニル基として例示した基が具体的に挙げられる。
　中でもＲy2は、
　置換基を有していてもよい炭素数２～１０の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）又は置換基を有していてもよい炭素数６～１０の芳香族炭化水素基がより好ましく、
　置換基を有していてもよい炭素数２～７の不飽和鎖状炭化水素基又は置換基を有していてもよい炭素数６～８の芳香族炭化水素基がさらに好ましく、
　置換基を有していてもよい炭素数２～７のアルケニル基又は置換基を有していてもよい炭素数６～８の芳香族炭化水素基がよりさらに好ましく、
　置換基を有していてもよいエテニル基又は置換基を有していてもよいフェニル基が特に好ましい。
　ｎｙ１～ｎｙ４は、それぞれ独立に、例えば０～２または４であり、好ましくは０～２、より好ましくは０～１、さらに好ましくは０である。
　Ｘy1～Ｘy4は、それぞれ独立に、－Ｒy4又はハロゲン原子が好ましく、炭素数１～１０の直鎖状又は分枝鎖状のアルキル基、或いはハロゲン原子がより好ましく、炭素数１～５の分枝鎖状アルキル基またはハロゲン原子がさらに好ましく、ｔｅｒｔ－ブチル基、フッ素原子、塩素原子、または臭素原子が特に好ましい。
　Ｙ1、Ｚy1、Ｚy2及びＺy3のうち少なくとも１つは硫黄原子を表し、Ｙ1が硫黄原子でありＺy1が酸素原子である態様、Ｙ1が酸素原子でありＺy1が硫黄原子である態様及びＺy2とＺy3とが硫黄原子である態様のうち少なくとも１つの態様を満足することが好ましい。ただし、Ｒy2が脂肪族不飽和炭化水素基である場合には、Ｚy2及びＺy3は単結合であることが好ましい。 In formula (YI),
R y1 is
An aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent is preferred,
more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent,
more preferably an aromatic hydrocarbon group having 6 to 8 carbon atoms which may have a substituent,
An optionally substituted phenyl group is particularly preferred.
Ry2 is
An optionally substituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms is preferred. Here, the aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms in preferred embodiments of R y2 and R y3 described later includes the groups described as the alkenyl group, alkynyl group, and unsaturated alicyclic hydrocarbon group described above. is mentioned. Examples of substituents that the C2-C20 aliphatic unsaturated hydrocarbon group may have include C2-C20 aliphatic unsaturated hydrocarbon groups represented by R x1 and R x3 . The groups described as the optional substituents can be mentioned. However, when the aliphatic unsaturated hydrocarbon group has an aromatic hydrocarbon group as a substituent, the total carbon number of the aliphatic unsaturated hydrocarbon group and the aromatic hydrocarbon group as a substituent is 20. It is below. Specific examples of the aliphatic unsaturated hydrocarbon group having an aromatic hydrocarbon group as a substituent include groups exemplified as arylalkenyl groups and arylalkynyl groups.
Among them, R y2 is
Unsaturated chain hydrocarbon groups of 2 to 10 carbon atoms which may have substituents (that is, alkenyl groups and alkynyl groups) or aromatic carbon atoms of 6 to 10 carbon atoms which may have substituents more preferably a hydrogen group,
An optionally substituted unsaturated chain hydrocarbon group having 2 to 7 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 8 carbon atoms is more preferable,
An optionally substituted alkenyl group having 2 to 7 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 8 carbon atoms is more preferable,
An optionally substituted ethenyl group or an optionally substituted phenyl group is particularly preferred.
ny1 to ny4 are each independently, for example, 0 to 2 or 4, preferably 0 to 2, more preferably 0 to 1, still more preferably 0.
X y1 to X y4 are each independently preferably -R y4 or a halogen atom, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, or a halogen atom, and 1 to 5 carbon atoms. is more preferred, and a tert-butyl group, a fluorine atom, a chlorine atom, or a bromine atom is particularly preferred.
At least one of Y 1 , Z y1 , Z y2 and Z y3 represents a sulfur atom, Y 1 is a sulfur atom and Z y1 is an oxygen atom, Y 1 is an oxygen atom and Z y1 is a sulfur atom and Z y2 and Z y3 are sulfur atoms. However, when Ry2 is an unsaturated aliphatic hydrocarbon group, Zy2 and Zy3 are preferably single bonds.
　式（ＹＩＩ）において、
　Ｒy3は、
　置換基を有していてもよい炭素数２～２０の脂肪族不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の芳香族炭化水素基が好ましく、
　置換基を有していてもよい炭素数２～１０の不飽和鎖状炭化水素基又は置換基を有していてもよい炭素数６～１０の芳香族炭化水素基がより好ましく、
　置換基を有していてもよい炭素数２～７の不飽和鎖状炭化水素基又は置換基を有していてもよい炭素数６～８の芳香族炭化水素基がさらに好ましく、
　置換基を有していてもよい炭素数２～７のアルケニル基又は置換基を有していてもよい炭素数６～８の芳香族炭化水素基がよりさらに好ましく、
　置換基を有していてもよいエテニル基又は置換基を有していてもよいフェニル基が特に好ましい。
　ｎｙ５～ｎｙ１２は、それぞれ独立に、例えば０～２または４であり、好ましくは０～２、より好ましくは０～１、さらに好ましくは０である。
　Ｘy5～Ｘy12は、それぞれ独立に、－Ｒy5又はハロゲン原子が好ましく、炭素数１～１０の直鎖状又は分枝鎖状のアルキル基、或いはハロゲン原子がより好ましく、炭素数１～５の分枝鎖状アルキル基またはハロゲン原子がさらに好ましく、ｔｅｒｔ－ブチル基、フッ素原子、塩素原子、または臭素原子が特に好ましい。
　Ｙ2、Ｚy4及びＺy5のうち少なくとも１つは硫黄原子を表す。ただし、Ｒy3が脂肪族不飽和炭化水素基である場合には、Ｚy5は単結合であることが好ましい。 In formula (YII),
Ry3 is
An optionally substituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable,
An optionally substituted unsaturated chain hydrocarbon group having 2 to 10 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms is more preferable,
An optionally substituted unsaturated chain hydrocarbon group having 2 to 7 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 8 carbon atoms is more preferable,
An optionally substituted alkenyl group having 2 to 7 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 8 carbon atoms is more preferable,
An optionally substituted ethenyl group or an optionally substituted phenyl group is particularly preferred.
ny5 to ny12 are each independently, for example, 0 to 2 or 4, preferably 0 to 2, more preferably 0 to 1, still more preferably 0.
X y5 to X y12 are each independently preferably -R y5 or a halogen atom, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, or a halogen atom, and 1 to 5 carbon atoms. is more preferred, and a tert-butyl group, a fluorine atom, a chlorine atom, or a bromine atom is particularly preferred.
At least one of Y2 , Zy4 and Zy5 represents a sulfur atom. However, when R y3 is an unsaturated aliphatic hydrocarbon group, Z y5 is preferably a single bond.
　式（ＹＩ）で表される化合物としては、式（ＹＩＡ）～式（ＹＩＥ）で表される化合物が挙げられる。 Compounds represented by formula (YI) include compounds represented by formulas (YIA) to (YIE).
Figure JPOXMLDOC01-appb-C000079
Figure JPOXMLDOC01-appb-C000079
Figure JPOXMLDOC01-appb-C000080
Figure JPOXMLDOC01-appb-C000080
Figure JPOXMLDOC01-appb-C000081
Figure JPOXMLDOC01-appb-C000081
Figure JPOXMLDOC01-appb-C000082
Figure JPOXMLDOC01-appb-C000082
Figure JPOXMLDOC01-appb-C000083
Figure JPOXMLDOC01-appb-C000083
［式（ＹＩＡ）～式（ＹＩＥ）中、Ｒy1、Ｒy2、Ｙ1、Ｚy1、Ｚy2及びＺy3は、前記に同じ。］ [In formulas (YIA) to (YIE), R y1 , R y2 , Y 1 , Z y1 , Z y2 and Z y3 are the same as above. ]
　式（ＹＩＡ）で表される化合物としては、例えば、表２６に示す式（ＹＩＡ－１）～式（ＹＩＡ－２４）で表される化合物が挙げられる。
　式（ＹＩＢ）で表される化合物としては、例えば、表２７に示す式（ＹＩＢ－１）～式（ＹＩＢ－２４）で表される化合物が挙げられる。
　式（ＹＩＣ）で表される化合物としては、例えば、表２８に示す式（ＹＩＣ－１）～式（ＹＩＣ－２４）で表される化合物が挙げられる。
　式（ＹＩＤ）で表される化合物としては、例えば、表２９に示す式（ＹＩＤ－１）～式（ＹＩＤ－２４）で表される化合物が挙げられる。
　式（ＹＩＥ）で表される化合物としては、例えば、表３０に示す式（ＹＩＥ－１）～式（ＹＩＥ－２４）で表される化合物が挙げられる。
　なお、表２６～表３０の「ｙｉ－１」はフェニル基を、「ｙｉ－２」はエテニル基を表す。 Examples of the compound represented by formula (YIA) include compounds represented by formulas (YIA-1) to (YIA-24) shown in Table 26.
Examples of the compound represented by formula (YIB) include compounds represented by formulas (YIB-1) to (YIB-24) shown in Table 27.
Examples of the compound represented by formula (YIC) include compounds represented by formulas (YIC-1) to (YIC-24) shown in Table 28.
Examples of the compound represented by formula (YID) include compounds represented by formulas (YID-1) to (YID-24) shown in Table 29.
Examples of the compound represented by formula (YIE) include compounds represented by formulas (YIE-1) to (YIE-24) shown in Table 30.
In Tables 26 to 30, "yi-1" represents a phenyl group, and "yi-2" represents an ethenyl group.
Figure JPOXMLDOC01-appb-T000084
Figure JPOXMLDOC01-appb-T000084
　式（ＹＩＡ）で表される化合物としては、
　式（ＹＩＡ－１）～式（ＹＩＡ－６）、式（ＹＩＡ－１３）～式（ＹＩＡ－１８）、式（ＹＩＡ－２１）、式（ＹＩＡ－２２）～式（ＹＩＡ－２４）で表される化合物が好ましく、
　式（ＹＩＡ－１）、式（ＹＩＡ－１３）、式（ＹＩＡ－２１）、式（ＹＩＡ－２３）、式（ＹＩＡ－２４）で表される化合物がより好ましい。 As the compound represented by the formula (YIA),
Formula (YIA-1) ~ Formula (YIA-6), Formula (YIA-13) ~ Formula (YIA-18), Formula (YIA-21), Formula (YIA-22) ~ Formula (YIA-24) are preferred,
Compounds represented by formula (YIA-1), formula (YIA-13), formula (YIA-21), formula (YIA-23) and formula (YIA-24) are more preferred.
Figure JPOXMLDOC01-appb-T000085
Figure JPOXMLDOC01-appb-T000085
　式（ＹＩＢ）で表される化合物としては、
　式（ＹＩＢ－１）～式（ＹＩＢ－６）、式（ＹＩＢ－１３）～式（ＹＩＢ－１８）、式（ＹＩＢ－２１）、式（ＹＩＢ－２２）～式（ＹＩＢ－２４）で表される化合物が好ましく、
　式（ＹＩＢ－１）、式（ＹＩＢ－１３）、式（ＹＩＢ－２１）、式（ＹＩＢ－２３）、式（ＹＩＢ－２４）で表される化合物がより好ましい。 As the compound represented by the formula (YIB),
Formula (YIB-1) ~ Formula (YIB-6), Formula (YIB-13) ~ Formula (YIB-18), Formula (YIB-21), Formula (YIB-22) ~ Formula (YIB-24) are preferred,
Compounds represented by formula (YIB-1), formula (YIB-13), formula (YIB-21), formula (YIB-23) and formula (YIB-24) are more preferred.
Figure JPOXMLDOC01-appb-T000086
Figure JPOXMLDOC01-appb-T000086
　式（ＹＩＣ）で表される化合物としては、
　式（ＹＩＣ－１）～式（ＹＩＣ－６）、式（ＹＩＣ－１３）～式（ＹＩＣ－１８）、式（ＹＩＣ－２１）、式（ＹＩＣ－２２）～式（ＹＩＣ－２４）で表される化合物が好ましく、
　式（ＹＩＣ－１）、式（ＹＩＣ－１３）、式（ＹＩＣ－２１）、式（ＹＩＣ－２３）、式（ＹＩＣ－２４）で表される化合物がより好ましい。 As the compound represented by the formula (YIC),
Formula (YIC-1) ~ Formula (YIC-6), Formula (YIC-13) ~ Formula (YIC-18), Formula (YIC-21), Formula (YIC-22) ~ Formula (YIC-24) are preferred,
Compounds represented by formula (YIC-1), formula (YIC-13), formula (YIC-21), formula (YIC-23) and formula (YIC-24) are more preferred.
Figure JPOXMLDOC01-appb-T000087
Figure JPOXMLDOC01-appb-T000087
　式（ＹＩＤ）で表される化合物としては、
　式（ＹＩＤ－１）～式（ＹＩＤ－６）、式（ＹＩＤ－１３）～式（ＹＩＤ－１８）、式（ＹＩＤ－２１）、式（ＹＩＤ－２２）～式（ＹＩＤ－２４）で表される化合物が好ましく、
　式（ＹＩＤ－１）、式（ＹＩＤ－１３）、式（ＹＩＤ－２１）、式（ＹＩＤ－２３）、式（ＹＩＤ－２４）で表される化合物がより好ましい。 As the compound represented by the formula (YID),
Formula (YID-1) ~ Formula (YID-6), Formula (YID-13) ~ Formula (YID-18), Formula (YID-21), Formula (YID-22) ~ Formula (YID-24) are preferred,
Compounds represented by formula (YID-1), formula (YID-13), formula (YID-21), formula (YID-23) and formula (YID-24) are more preferred.
Figure JPOXMLDOC01-appb-T000088
Figure JPOXMLDOC01-appb-T000088
　式（ＹＩＥ）で表される化合物としては、
　式（ＹＩＥ－１）～式（ＹＩＥ－６）、式（ＹＩＥ－１３）～式（ＹＩＥ－１８）、式（ＹＩＥ－２１）、式（ＹＩＥ－２２）～式（ＹＩＥ－２４）で表される化合物が好ましく、
　式（ＹＩＥ－１）、式（ＹＩＥ－１３）、式（ＹＩＥ－２１）、式（ＹＩＥ－２３）、式（ＹＩＥ－２４）で表される化合物がより好ましい。 As the compound represented by the formula (YIE),
Formula (YIE-1) ~ Formula (YIE-6), Formula (YIE-13) ~ Formula (YIE-18), Formula (YIE-21), Formula (YIE-22) ~ Formula (YIE-24) are preferred,
Compounds represented by Formula (YIE-1), Formula (YIE-13), Formula (YIE-21), Formula (YIE-23) and Formula (YIE-24) are more preferred.
　式（ＹＩＩ）で表される化合物としては、式（ＹＩＩＡ)～式（ＹＩＩＥ）で表される化合物が挙げられる。 Compounds represented by formula (YII) include compounds represented by formulas (YIIA) to (YIIE).
Figure JPOXMLDOC01-appb-C000089
Figure JPOXMLDOC01-appb-C000089
Figure JPOXMLDOC01-appb-C000090
Figure JPOXMLDOC01-appb-C000090
Figure JPOXMLDOC01-appb-C000091
Figure JPOXMLDOC01-appb-C000091
Figure JPOXMLDOC01-appb-C000092
Figure JPOXMLDOC01-appb-C000092
Figure JPOXMLDOC01-appb-C000093
Figure JPOXMLDOC01-appb-C000093
［式（ＹＩＩＡ)～式（ＹＩＩＥ）中、Ｒy3、Ｙ2、Ｚy4及びＺy5は、前記に同じ。］ [In formulas (YIIA) to (YIIE), R y3 , Y 2 , Z y4 and Z y5 are the same as above. ]
　式（ＹＩＩＡ)で表される化合物としては、例えば、表３１に示す式（ＹＩＩＡ－１）
～式（ＹＩＩＡ－１３）で表される化合物が挙げられる。
　式（ＹＩＩＢ）で表される化合物としては、例えば、表３２に示す式（ＹＩＩＢ－１）～式（ＹＩＩＢ－１３）で表される化合物が挙げられる。
　式（ＹＩＩＣ）で表される化合物としては、例えば、表３３に示す式（ＹＩＩＣ－１）～式（ＹＩＩＣ－１３）で表される化合物が挙げられる。
　式（ＹＩＩＤ）で表される化合物としては、例えば、表３４に示す式（ＹＩＩＤ－１）～式（ＹＩＩＤ－１３）で表される化合物が挙げられる。
　式（ＹＩＩＥ）で表される化合物としては、例えば、表３５に示す式（ＹＩＩＥ－１）～式（ＹＩＩＥ－１３）で表される化合物が挙げられる。
　なお、表３１～表３５中の「ｙｉ－１」はフェニル基を、「ｙｉ－２」はエテニル基を表す。 Compounds represented by formula (YIIA) include, for example, formula (YIIA-1) shown in Table 31
to the compound represented by the formula (YIIA-13).
Examples of the compound represented by formula (YIIB) include compounds represented by formulas (YIIB-1) to (YIIB-13) shown in Table 32.
Examples of the compound represented by formula (YIIC) include compounds represented by formulas (YIIC-1) to (YIIC-13) shown in Table 33.
Examples of the compound represented by the formula (YIID) include compounds represented by the formulas (YIID-1) to (YIID-13) shown in Table 34.
Examples of the compound represented by formula (YIIE) include compounds represented by formulas (YIIE-1) to (YIIE-13) shown in Table 35.
In Tables 31 to 35, "yi-1" represents a phenyl group and "yi-2" represents an ethenyl group.
Figure JPOXMLDOC01-appb-T000094
Figure JPOXMLDOC01-appb-T000094
　式（ＹＩＩＡ)で表される化合物としては、
　式（ＹＩＩＡ－１）、式（ＹＩＩＡ－２）、式（ＹＩＩＡ－８）、式（ＹＩＩＡ－９）、式（ＹＩＩＡ－１２）、式（ＹＩＩＡ－１３）で表される化合物が好ましく、
　式（ＹＩＩＡ－１）、式（ＹＩＩＡ－８）、式（ＹＩＩＡ－１２）、式（ＹＩＩＡ－１３）で表される化合物がより好ましい。 As the compound represented by the formula (YIIA),
Compounds represented by formula (YIIA-1), formula (YIIA-2), formula (YIIA-8), formula (YIIA-9), formula (YIIA-12), and formula (YIIA-13) are preferred,
Compounds represented by formula (YIIA-1), formula (YIIA-8), formula (YIIA-12), and formula (YIIA-13) are more preferred.
Figure JPOXMLDOC01-appb-T000095
Figure JPOXMLDOC01-appb-T000095
　式（ＹＩＩＢ）で表される化合物としては、
　式（ＹＩＩＢ－１）、式（ＹＩＩＢ－２）、式（ＹＩＩＢ－８）、式（ＹＩＩＢ－９）、式（ＹＩＩＢ－１２）、式（ＹＩＩＢ－１３）で表される化合物が好ましく、
　式（ＹＩＩＢ－１）、式（ＹＩＩＢ－８）、式（ＹＩＩＢ－１２）、式（ＹＩＩＢ－１３）で表される化合物がより好ましい。 As the compound represented by the formula (YIIB),
Compounds represented by formula (YIIB-1), formula (YIIB-2), formula (YIIB-8), formula (YIIB-9), formula (YIIB-12), and formula (YIIB-13) are preferred,
Compounds represented by formula (YIIB-1), formula (YIIB-8), formula (YIIB-12), and formula (YIIB-13) are more preferable.
Figure JPOXMLDOC01-appb-T000096
Figure JPOXMLDOC01-appb-T000096
　式（ＹＩＩＣ）で表される化合物としては、
　式（ＹＩＩＣ－１）、式（ＹＩＩＣ－２）、式（ＹＩＩＣ－８）、式（ＹＩＩＣ－９）、式（ＹＩＩＣ－１２）、式（ＹＩＩＣ－１３）で表される化合物が好ましく、
　式（ＹＩＩＣ－１）、式（ＹＩＩＣ－８）、式（ＹＩＩＣ－１２）、式（ＹＩＩＣ－１３）で表される化合物がより好ましい。 As the compound represented by the formula (YIIC),
Compounds represented by formula (YIIC-1), formula (YIIC-2), formula (YIIC-8), formula (YIIC-9), formula (YIIC-12), and formula (YIIC-13) are preferred,
Compounds represented by formula (YIIC-1), formula (YIIC-8), formula (YIIC-12), and formula (YIIC-13) are more preferred.
Figure JPOXMLDOC01-appb-T000097
Figure JPOXMLDOC01-appb-T000097
　式（ＹＩＩＤ）で表される化合物としては、
　式（ＹＩＩＤ－１）、式（ＹＩＩＤ－２）、式（ＹＩＩＤ－８）、式（ＹＩＩＤ－９）、式（ＹＩＩＤ－１２）、式（ＹＩＩＤ－１３）で表される化合物が好ましく、
　式（ＹＩＩＤ－１）、式（ＹＩＩＤ－８）、式（ＹＩＩＤ－１２）、式（ＹＩＩＤ－１３）で表される化合物がより好ましい。 As the compound represented by the formula (YIID),
Compounds represented by formula (YIID-1), formula (YIID-2), formula (YIID-8), formula (YIID-9), formula (YIID-12), and formula (YIID-13) are preferred,
Compounds represented by formula (YIID-1), formula (YIID-8), formula (YIID-12), and formula (YIID-13) are more preferred.
Figure JPOXMLDOC01-appb-T000098
Figure JPOXMLDOC01-appb-T000098
　式（ＹＩＩＥ）で表される化合物としては、
　式（ＹＩＩＥ－１）、式（ＹＩＩＥ－２）、式（ＹＩＩＥ－８）、式（ＹＩＩＥ－９）、式（ＹＩＩＥ－１２）、式（ＹＩＩＥ－１３）で表される化合物が好ましく、
　式（ＹＩＩＥ－１）、式（ＹＩＩＥ－８）、式（ＹＩＩＥ－１２）、式（ＹＩＩＥ－１３）で表される化合物がより好ましい。 As the compound represented by the formula (YIIE),
Compounds represented by formula (YIIE-1), formula (YIIE-2), formula (YIIE-8), formula (YIIE-9), formula (YIIE-12), and formula (YIIE-13) are preferred,
Compounds represented by formula (YIIE-1), formula (YIIE-8), formula (YIIE-12), and formula (YIIE-13) are more preferred.
　式（ＹＩ）で表される化合物は、例えば、式（ＹＩＩＩ）で表される化合物と、式（ＹＩＶ）で表される化合物を適宜反応させることにより製造できる。
　また式（ＹＩＩ）で表される化合物は、例えば、式（ＹＩＩＩａ）及び式（ＹＩＩＩｂ）で表される化合物と、式（ＹＶ）で表される化合物を適宜反応させることにより製造できる。 The compound represented by formula (YI) can be produced, for example, by appropriately reacting a compound represented by formula (YIII) with a compound represented by formula (YIV).
Further, the compound represented by the formula (YII) can be produced, for example, by appropriately reacting the compounds represented by the formulas (YIIIa) and (YIIIb) with the compound represented by the formula (YV).
Figure JPOXMLDOC01-appb-C000099
Figure JPOXMLDOC01-appb-C000099
［式（ＹＩ）、式（ＹＩＩＩ）及び式（ＹＩＶ）中、Ｒy1、Ｒy2、Ｙ1、Ｚy1、Ｚy2、Ｚy3、Ｘy1～Ｘy4及びｎｙ１～ｎｙ４は、前記に同じ。］ [In formula (YI), formula (YIII) and formula (YIV), R y1 , R y2 , Y 1 , Z y1 , Z y2 , Z y3 , X y1 to X y4 and ny1 to ny4 are the same as above. ]
Figure JPOXMLDOC01-appb-C000100
Figure JPOXMLDOC01-appb-C000100
［式（ＹＩＩ）、式（ＹＩＩＩａ）、式（ＹＩＩＩｂ）及び式（ＹＶ）中、Ｒy3、Ｙ2、Ｚy4、Ｚy5、Ｘy5～Ｘy12、及びｎｙ５～ｎｙ１２は、前記に同じ。］ [In formula (YII), formula (YIIIa), formula (YIIIb) and formula (YV), R y3 , Y 2 , Z y4 , Z y5 , X y5 to X y12 and ny5 to ny12 are the same as above. ]
　前記フタロシアニン化合物は、分散剤を含有させて分散処理を行うことで、分散剤溶液の中で均一に分散した状態の分散液とすることができる。フタロシアニン化合物は、単独で分散処理してもよいし、複数種を混合して分散処理してもよい。 The phthalocyanine compound can be dispersed uniformly in the dispersant solution by adding a dispersant and performing a dispersion treatment. The phthalocyanine compound may be subjected to dispersion treatment alone, or may be mixed with a plurality of types and subjected to dispersion treatment.
　分散剤としては、後述する顔料分散剤と同じものが挙げられる。 As the dispersant, the same as the pigment dispersant described later can be used.
　分散剤を用いる場合、その使用量は、分散液におけるフタロシアニン化合物１００質量部に対して、好ましくは１０質量部以上２００質量部以下であり、より好ましくは１５質量部以上１８０質量部以下、さらに好ましくは２０質量部以上１６０質量部以下である。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分散液が得られる傾向がある。 When a dispersant is used, the amount used is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 15 parts by mass or more and 180 parts by mass or less, and even more preferably, relative to 100 parts by mass of the phthalocyanine compound in the dispersion. is 20 parts by mass or more and 160 parts by mass or less. When the amount of the dispersant used is within the above range, there is a tendency to obtain a more uniformly dispersed liquid dispersion.
　フタロシアニン化合物の含有率は、着色硬化性組成物の固形分の総量中、好ましくは０．５～７０質量％、より好ましくは１～５５質量％、さらに好ましくは２～５０質量％である。また、フタロシアニン化合物の含有率は、着色硬化性組成物の固形分の総量中、１０～５０質量％であってもよい。
　なお、本明細書において「固形分の総量」とは、本発明の着色硬化性組成物から溶剤を除いた成分の合計量をいう。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、ガスクロマトグラフィー等の公知の分析手段により測定することができる。 The content of the phthalocyanine compound is preferably 0.5 to 70% by mass, more preferably 1 to 55% by mass, still more preferably 2 to 50% by mass, based on the total solid content of the colored curable composition. Also, the content of the phthalocyanine compound may be 10 to 50% by mass based on the total solid content of the colored curable composition.
As used herein, the term "total amount of solids" refers to the total amount of components of the colored curable composition of the present invention excluding the solvent. The total amount of solids and the content of each component relative thereto can be measured by known analysis means such as liquid chromatography and gas chromatography.
　またフタロシアニン化合物の含有率は、着色剤（Ａ）の総量中、１質量％以上であることが好ましく、より好ましくは３質量％以上、さらに好ましくは５質量％以上、よりさらに好ましくは１０質量％以上、特に好ましくは５０質量％以上である。また前記含有率の上限は特に限定されないが、１００質量％であってもよく、８０質量％であってもよく、７０質量％であってもよく、６０質量％であってもよい。 The content of the phthalocyanine compound is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and even more preferably 10% by mass, based on the total amount of the colorant (A). above, and particularly preferably at least 50% by mass. The upper limit of the content is not particularly limited, but may be 100% by mass, 80% by mass, 70% by mass, or 60% by mass.
　着色剤（Ａ）は、フタロシアニン化合物とは異なる着色剤（以下、着色剤（Ａ２）という場合がある）をさらに含んでいてもよい。 The coloring agent (A) may further contain a coloring agent different from the phthalocyanine compound (hereinafter sometimes referred to as coloring agent (A2)).
　着色剤（Ａ２）は、染料及び顔料のいずれであってもよく、それらの混合物であってもよい。 The coloring agent (A2) may be either a dye or a pigment, or a mixture thereof.
　染料としては、例えば、カラーインデックス（The Society of Dyers and Colourists出版）において顔料以外で色相を有するもの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。 Dyes include, for example, compounds classified as having hues other than pigments in the Color Index (published by The Society of Dyers and Colourists), and known dyes listed in Stain Note (Shikisensha). be done.
　染料としては、例えば、アゾ染料、シアニン染料、トリフェニルメタン染料、チアゾール染料、オキサジン染料、キノフタロン染料、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、キノリン染料及びニトロ染料等を使用してもよくそれぞれ公知の染料が使用される。 Examples of dyes include azo dyes, cyanine dyes, triphenylmethane dyes, thiazole dyes, oxazine dyes, quinophthalone dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, Coumarin dyes, quinoline dyes, nitro dyes, and the like may be used, and known dyes are used.
　染料としては、具体的には、Ｃ．Ｉ．ソルベントイエロー４（以下、Ｃ．Ｉ．ソルベントイエローの記載を省略し、番号のみの記載とする。他も同様である。）、１４、１５、２３、２４、３８、６２、６３、６８、８２、９４、９９、１１７、１６２、１６３、１６７、１８９；
　Ｃ．Ｉ．ソルベントレッド１１１、１２５、１３０、１４３、１４５、１４６、１５０、１５１、１５５、１６８、１６９、１７２、１７５、１８１、２０７、２２２、２２７、２３０、２４５、２４７；
　Ｃ．Ｉ．ソルベントオレンジ２、７、１１、１５、２６、５６、７７、８６；
　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、４５、５８、５９、５９：１、６３、６８、６９、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、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、５７、６６、７３、７６、８０、８８、９７、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、３０８、３１２、３１５、３１６、３３９、３４１、３４５、３４６、３４９、３８２、３８３、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、１６９、１７３；
　Ｃ．Ｉ．アシッドバイオレット６Ｂ、７、１５、１６、１７、１９、２１、２３、２４、２５、３４、３８、４９、７２；
　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、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、３３、３４、３５、３８、３９、４３、４７、５０、５４、５８、６８、６９、７０、７１、８６、９３、９４、９５、９８、１０２、１０８、１０９、１２９、１３６、１３８、１４１；
　Ｃ．Ｉ．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、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、１９０、１９２、１９３、１９４、１９５、１９６、１９８、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、７７、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、６０等のＣ．Ｉ．ディスパース染料、
　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、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、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．バット染料等が挙げられる。
　これらの染料は、各色について１種の染料又は複数の染料を使用してもよく、各色の染料を組み合わせてもよい。 Specific examples of dyes include C.I. I. Solvent Yellow 4 (hereinafter, the description of C.I. Solvent Yellow is omitted and only the number is described. The same applies to others.), 14, 15, 23, 24, 38, 62, 63, 68, 82 , 94, 99, 117, 162, 163, 167, 189;
C. I. Solvent Red 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86;
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, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
C. I. C.I. I. solvent dyes,
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 57, 66, 73, 76, 80, 88, 97, 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, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 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, 169, 173;
C. I. Acid Violet 6B, 7, 15, 16, 17, 19, 21, 23, 24, 25, 34, 38, 49, 72;
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, 210, 213, 229, 234, 236, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;
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 and the like. I. acid dye,
C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
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, 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, 190, 192, 193, 194, 195, 196, 198, 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 Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like. I. direct dye,
C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse Violet 26, 27;
C. I. C.I. I. disperse dyes,
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 Green 1 and other C.I. I. basic dye,
C. I. Reactive Yellow 2, 76, 116;
C. I. Reactive Orange 16;
C. I. C.I. I. reactive dyes,
C. I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern Tread 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 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. Modant 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. Modant 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, 83, 84;
C. I. C.I. I. modant dye,
C. I. C.I. I. and vat dyes.
As for these dyes, one type of dye or a plurality of dyes may be used for each color, and dyes of each color may be combined.
　顔料としては、例えば、カラーインデックス（Ｔｈｅ　Ｓｏｃｉｅｔｙ　ｏｆ　Ｄｙｅｒｓ　ａｎｄ　Ｃｏｌｏｕｒｉｓｔｓ出版）でピグメントに分類されている顔料が挙げられ、以下の顔料を例示できる。 Examples of pigments include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colorists), and the following pigments can be exemplified.
　黄色顔料：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等
　オレンジ色顔料：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
　赤色顔料：Ｃ．Ｉ．ピグメントレッド９、９７、１０５、１２２、１４４、１４９、１６６、１６８、１７６、１７７、１８０、１９２、２０９、２１５、２１６、２４２、２５４、２５５、２６４、２６５等
　紫色顔料：Ｃ．Ｉ．ピグメントバイオレット１９、２３、２９、３２、３６、３８等
　これらの顔料は、各色について１種の顔料又は複数の顔料を使用してもよく、各色の顔料を組み合わせてもよい。 Yellow pigment: C.I. 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, etc. Orange pigment: C.I. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, etc. Red pigment: C.I. I. Pigment Red 9, 97, 105, 122, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 242, 254, 255, 264, 265, etc. Purple pigment: C.I. I. Pigment Violet 19, 23, 29, 32, 36, 38, etc. As for these pigments, one type of pigment or a plurality of pigments may be used for each color, and pigments of each color may be combined.
　顔料は、必要に応じて、ロジン処理、酸性基または塩基性基が導入された顔料誘導体等を用いた表面処理、高分子化合物等による顔料表面へのグラフト処理、硫酸微粒化法等による微粒化処理、不純物を除去するための有機溶剤や水等による洗浄処理、イオン性不純物のイオン交換法等による除去処理等が施されていてもよい。顔料の粒径は、略均一であることが好ましい。顔料は、顔料分散剤を含有させて分散処理を行うことで、分散剤溶液の中で均一に分散した状態の分散液とすることができる。顔料は、単独で分散処理してもよいし、複数種を混合して分散処理してもよい。 If necessary, the pigment is subjected to rosin treatment, surface treatment using a pigment derivative into which an acidic or basic group has been introduced, graft treatment to the pigment surface with a polymer compound, etc., atomization by a sulfuric acid atomization method, etc. Treatment, washing treatment with an organic solvent or water for removing impurities, removal treatment by an ion exchange method for ionic impurities, or the like may be performed. It is preferable that the particle size of the pigment is substantially uniform. The pigment can be dispersed uniformly in the dispersant solution by adding a pigment dispersant and performing a dispersion treatment. The pigments may be subjected to dispersion treatment alone, or may be dispersed by mixing plural kinds of pigments.
　顔料分散剤としては、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、単独で又は二種以上を組合せて用いてもよい。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）、Ｄｉｓｐｅｒｂｙｋ（登録商標）、ＢＹＫ（登録商標）（ビックケミー社製）等が挙げられる。 Examples of pigment dispersants include surfactants, which may be cationic, anionic, nonionic or amphoteric surfactants. Specific examples include surfactants such as polyester-based, polyamine-based and acrylic-based surfactants. These dispersants may be used alone or in combination of two or more. As the dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), and EFKA (registered trademark). (manufactured by BASF), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (registered trademark), BYK (registered trademark) (manufactured by BYK-Chemie) and the like.
　顔料分散剤を用いる場合、その使用量は、分散液における顔料１００質量部に対して、好ましくは１０質量部以上２００質量部以下であり、より好ましくは１５質量部以上１８０質量部以下、さらに好ましくは２０質量部以上１６０質量部以下である。顔料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分散液が得られる傾向がある。 When a pigment dispersant is used, the amount used is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 15 parts by mass or more and 180 parts by mass or less, and still more preferably 100 parts by mass of the pigment in the dispersion. is 20 parts by mass or more and 160 parts by mass or less. When the amount of the pigment dispersant used is within the above range, there is a tendency to obtain a dispersion with a more uniform dispersion state.
　着色剤（Ａ）が着色剤（Ａ２）を含む場合、着色剤（Ａ２）の含有率は、着色剤（Ａ）の総量中、好ましくは１～９９質量％、より好ましくは１～８０質量％、さらに好ましくは２０～５０質量％である。また着色剤（Ａ２）の含有率は、着色剤（Ａ）の総量中、２０～９７質量％であってもよく、３０～９５質量％であってもよく、４０～９０質量％であってもよい、 When the colorant (A) contains the colorant (A2), the content of the colorant (A2) is preferably 1 to 99% by mass, more preferably 1 to 80% by mass, based on the total amount of the colorant (A). , more preferably 20 to 50% by mass. The content of the colorant (A2) may be 20 to 97% by mass, 30 to 95% by mass, or 40 to 90% by mass in the total amount of the colorant (A). good,
　着色硬化性組成物中の着色剤（Ａ）の含有率は、固形分の総量に対して、好ましくは０．５～８０質量％、より好ましくは５～７０質量％、さらに好ましくは１０～５５質量％である。着色剤（Ａ）の含有率が前記の範囲内であると、所望とする分光や色濃度をより得やすくなる。 The content of the coloring agent (A) in the colored curable composition is preferably 0.5 to 80% by mass, more preferably 5 to 70% by mass, more preferably 10 to 55% by mass, based on the total amount of solids. % by mass. When the content of the coloring agent (A) is within the above range, it becomes easier to obtain the desired spectrum and color density.
＜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］等が挙げられる。
　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（ａ）（以下「（ａ）」という場合がある）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）との共重合体；
　樹脂［Ｋ２］；（ａ）と（ｂ）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）との共重合体；
　樹脂［Ｋ３］；（ａ）と（ｃ）との共重合体；
　樹脂［Ｋ４］；（ａ）と（ｃ）との共重合体に（ｂ）を反応させた樹脂；
　樹脂［Ｋ５］；（ｂ）と（ｃ）との共重合体に（ａ）を反応させた樹脂；
　樹脂［Ｋ６］；（ｂ）と（ｃ）との共重合体に（ａ）を反応させ、さらに多価カルボン酸及び／又はカルボン酸無水物を反応させた樹脂。 <Resin (B)>
Although the resin (B) is not particularly limited, it is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].
Resin [K1]: at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter sometimes referred to as "(a)"), and a cyclic ether having 2 to 4 carbon atoms A copolymer with a monomer (b) having a structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)");
Resin [K2]; (a) and (b), and monomer (c) copolymerizable with (a) (but different from (a) and (b)) (hereinafter “(c)” may be called) and a copolymer;
Resin [K3]; copolymer of (a) and (c);
Resin [K4]; a resin obtained by reacting a copolymer of (a) and (c) with (b);
Resin [K5]; a resin obtained by reacting (a) with a copolymer of (b) and (c);
Resin [K6]: A resin obtained by reacting (a) with a copolymer of (b) and (c), and further reacting a polyvalent carboxylic acid and/or a carboxylic acid anhydride.
　（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;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;
methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 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, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other bicyclounsaturated compounds containing a carboxy group;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as 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, mono[2-(meth)acryloyloxyethyl] phthalate kind;
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, and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an alkaline aqueous 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 (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. say. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.
In this specification, "(meth)acrylic acid" represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as "(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 having an oxetanyl group and an ethylenically unsaturated bond, a monomer (b2) (hereinafter sometimes referred to as "(b2)"), a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), etc. mentioned.
　（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。 As (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as "(b1-1)" ), and a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).
　（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-methylglycidyl (meth)acrylate, β-ethylglycidyl (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(glycidyloxymethyl)styrene , 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene , 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris (glycidyloxymethyl)styrene and the like.
　（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）、３，４－エポキシトリシクロ［５．２．１．０2,6］デシル（メタ）アクリレート、式（Ｒ１）で表される化合物及び式（Ｒ２）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 (eg, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (eg, Cychromer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (eg, Cychromer M100; manufactured by Daicel Corporation), 3,4-epoxytricyclo [5.2.1. 0 2,6 ]decyl (meth)acrylate, a compound represented by formula (R1), a compound represented by formula (R2), and the like.
Figure JPOXMLDOC01-appb-C000101
Figure JPOXMLDOC01-appb-C000101
［式（Ｒ１）及び式（Ｒ２）中、Ｒra及びＲrb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。
　Ｘra及びＸrbは、単結合、＊－Ｒrc－、＊－Ｒrc－Ｏ－、＊－Ｒrc－Ｓ－又は＊－Ｒrc－ＮＨ－を表す。
　Ｒrc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 the formulas (R1) and (R2), R ra and R rb represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. may
X ra and X rb represent a single bond, *-R rc -, *-R rc -O-, *-R rc -S- or *-R rc -NH-.
R rc represents an alkanediyl group having 1 to 6 carbon atoms.
* represents a bond with 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。
　Ｒra及びＲrb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 alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.
Alkyl groups in which hydrogen atoms are substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.
R ra and R rb preferably include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, more preferably a hydrogen atom and 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。
　Ｘra及びＸrb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）。 The alkanediyl group includes methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane- A 1,6-diyl group and the like can be mentioned.
X ra and X rb are preferably a single bond, a methylene group, an ethylene group, *--CH 2 --O-- and *--CH 2 CH 2 --O--, more preferably a single bond and *--CH 2 CH 2 --O-- (* represents a bond with O).
　式（Ｒ１）で表される化合物としては、式（Ｒ１－１）～式（Ｒ１－１５）のいずれかで表される化合物等が挙げられる。中でも、式（Ｒ１－１）、式（Ｒ１－３）、式（Ｒ１－５）、式（Ｒ１－７）、式（Ｒ１－９）又は式（Ｒ１－１１）～式（Ｒ１－１５）で表される化合物が好ましく、式（Ｒ１－１）、式（Ｒ１－７）、式（Ｒ１－９）又は式（Ｒ１－１５）で表される化合物がより好ましい。 Examples of the compound represented by formula (R1) include compounds represented by any one of formulas (R1-1) to (R1-15). Among them, formula (R1-1), formula (R1-3), formula (R1-5), formula (R1-7), formula (R1-9) or formula (R1-11) to formula (R1-15) A compound represented by is preferable, and a compound represented by formula (R1-1), formula (R1-7), formula (R1-9) or formula (R1-15) is more preferable.
Figure JPOXMLDOC01-appb-C000102
Figure JPOXMLDOC01-appb-C000102
Figure JPOXMLDOC01-appb-C000103
Figure JPOXMLDOC01-appb-C000103
　式（Ｒ２）で表される化合物としては、式（Ｒ２－１）～式（Ｒ２－１５）のいずれかで表される化合物等が挙げられる。中でも、式（Ｒ２－１）、式（Ｒ２－３）、式（Ｒ２－５）、式（Ｒ２－７）、式（Ｒ２－９）又は式（Ｒ２－１１）～式（Ｒ２－１５）で表される化合物が好ましく、式（Ｒ２－１）、式（Ｒ２－７）、式（Ｒ２－９）又は式（Ｒ２－１５）で表される化合物がより好ましい。 Examples of the compound represented by formula (R2) include compounds represented by any one of formulas (R2-1) to (R2-15). Among them, formula (R2-1), formula (R2-3), formula (R2-5), formula (R2-7), formula (R2-9) or formula (R2-11) to formula (R2-15) A compound represented by is preferable, and a compound represented by formula (R2-1), formula (R2-7), formula (R2-9) or formula (R2-15) is more preferable.
Figure JPOXMLDOC01-appb-C000104
Figure JPOXMLDOC01-appb-C000104
Figure JPOXMLDOC01-appb-C000105
Figure JPOXMLDOC01-appb-C000105
　（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。 (b2) is more preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group. (b2) includes 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。 (b3) is more preferably a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group. Specific examples of (b3) include tetrahydrofurfuryl acrylate (eg, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.
　（ｂ）としては、得られるカラーフィルタの耐熱性、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、着色硬化性組成物の保存安定性がより優れるという点で、（ｂ１－２）がより好ましい。 (b) is preferably (b1) in that the heat resistance, chemical resistance, etc. of the obtained color filter can be made more reliable. Furthermore, (b1-2) is more preferable in that the storage stability of the colored curable composition is more excellent.
　（ｃ）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、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。）、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、イソボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、アリル（メタ）アクリレート、プロパルギル（メタ）アクリレート、フェニル（メタ）アクリレート、ナフチル（メタ）アクリレート、ベンジル（メタ）アクリレート等の（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；
　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；
　ビシクロ［２．２．１］ヘプト－２－エン、５－メチルビシクロ［２．２．１］ヘプト－２－エン、５－エチルビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシメチルビシクロ［２．２．１］ヘプト－２－エン、５－（２’－ヒドロキシエチル）ビシクロ［２．２．１］ヘプト－２－エン、５－メトキシビシクロ［２．２．１］ヘプト－２－エン、５－エトキシビシクロ［２．２．１］ヘプト－２－エン、５，６－ジヒドロキシビシクロ［２．２．１］ヘプト－２－エン、５，６－ジ（ヒドロキシメチル）ビシクロ［２．２．１］ヘプト－２－エン、５，６－ジ（２’－ヒドロキシエチル）ビシクロ［２．２．１］ヘプト－２－エン、５，６－ジメトキシビシクロ［２．２．１］ヘプト－２－エン、５，６－ジエトキシビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシ－５－メチルビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシ－５－エチルビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシメチル－５－メチルビシクロ［２．２．１］ヘプト－２－エン、５－ｔｅｒｔ－ブトキシカルボニルビシクロ［２．２．１］ヘプト－２－エン、５－シクロヘキシルオキシカルボニルビシクロ［２．２．１］ヘプト－２－エン、５－フェノキシカルボニルビシクロ［２．２．１］ヘプト－２－エン、５，６－ビス（ｔｅｒｔ－ブトキシカルボニル）ビシクロ［２．２．１］ヘプト－２－エン、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；
　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；
　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、アクリロニトリル、メタクリロニトリル、塩化ビニル、塩化ビニリデン、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。
　（ｃ）としては、２－エチルヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ベンジル（メタ）アクリレート、スチレン、ビニルトルエン、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド、Ｎ－ベンジルマレイミド、ビシクロ［２．２．１］ヘプト－２－エン等が好ましく、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、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド、Ｎ－ベンジルマレイミド、ビシクロ［２．２．１］ヘプト－２－エン等がより好ましい。 (c) includes, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth) Acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 ]Decan-8-yl (meth)acrylate (in the technical field, it is commonly referred to as “dicyclopentanyl (meth)acrylate”. In the case of “tricyclodecyl (meth)acrylate” ), tricyclo[5.2.1.0 2,6 ]decen-8-yl (meth)acrylate (in the art, it is commonly called “dicyclopentenyl (meth)acrylate”. ), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth) acrylic acid esters such as (meth) acrylate;
Hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;
bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5- Hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2′-hydroxyethyl)bicyclo[2.2.1] Hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2 .1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2′-hydroxyethyl)bicyclo[2.2. 1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy -5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2 .2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyl oxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 - dicarbonylimide derivatives such as maleimidopropionate, N-(9-acridinyl)maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , isoprene, 2,3-dimethyl-1,3-butadiene, and the like.
(c) includes 2-ethylhexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, benzyl (meth)acrylate, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] Hept-2-ene and the like are preferred, and from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2 .2.1]hept-2-ene and the like are more preferred.
　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。
　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、及び得られるカラー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 the total structural units constituting the resin [K1] is
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (b); 40 to 98 mol%
is preferably
Structural unit derived from (a); 10 to 50 mol%
Structural unit derived from (b); 50 to 90 mol%
is more preferable.
When the ratio of the structural units of the resin [K1] is within the above range, the storage stability of the colored curable composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter tend to be excellent. There is
　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。 The resin [K1] is, for example, the method described in the document "Experimental Methods for Polymer Synthesis" (written by Takayuki Otsu, Published by Kagaku Dojin, 1st Edition, 1st Edition, March 1, 1972) and the document It can be manufactured with reference to the cited document described in .
　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、撹拌しながら、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、溶剤（Ｇ）として後述する溶剤等が挙げられる。 Specifically, predetermined amounts of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and, for example, by replacing oxygen with nitrogen, a deoxygenated atmosphere is created, and while stirring, A method of heating and keeping warm can be mentioned. The polymerization initiator, solvent, and the like used here are not particularly limited, and those commonly used in the relevant 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.). As the solvent, any solvent can be used as long as it dissolves each monomer, and examples of the solvent (G) include the solvents described later.
　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、着色硬化性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着色硬化性組成物の調製に使用することができるため、着色硬化性組成物の製造工程を簡略化することができる。 The obtained copolymer may be used as a solution after the reaction as it is, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. You can use things. In particular, by using the solvent contained in the colored curable composition as a solvent during this polymerization, the solution after the reaction can be used as it is for the preparation of the colored curable composition, so that the colored curable composition The manufacturing process of things 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；２～４５モル％
（ｂ）に由来する構造単位；２～９５モル％
（ｃ）に由来する構造単位；１～６５モル％
であることが好ましく、
（ａ）に由来する構造単位；５～４０モル％
（ｂ）に由来する構造単位；５～８０モル％
（ｃ）に由来する構造単位；５～６０モル％
であることがより好ましい。
　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、得られるカラー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 the total structural units constituting the resin [K2] is
Structural unit derived from (a); 2 to 45 mol%
Structural unit derived from (b); 2 to 95 mol%
Structural unit derived from (c); 1 to 65 mol%
is preferably
Structural unit derived from (a); 5 to 40 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (c); 5 to 60 mol%
is more preferable.
When the ratio of the structural units of the resin [K2] is within the above range, the storage stability of the colored curable composition, developability when forming a colored pattern, and the solvent resistance and heat resistance of the resulting color filter are improved. It tends to have excellent toughness and mechanical strength.
　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。 The resin [K2] can be produced, for example, in the same manner as the method for producing the 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], the ratio of the structural units derived from each of the total structural units constituting the resin [K3] is
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (c); 40 to 98 mol%
is preferably
Structural unit derived from (a); 10 to 50 mol%
Structural unit derived from (c); 50 to 90 mol%
is more preferable.
Resin [K3] can be produced, for example, in the same manner as the method for producing resin [K1].
　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] is a carboxylic acid and/or carboxylic acid anhydride obtained by obtaining a copolymer of (a) and (c), and having (a) a cyclic ether having 2 to 4 carbon atoms possessed by (b). It can be produced by adding to
First, a copolymer of (a) and (c) is produced in the same manner as the method for producing resin [K1]. In this case, the ratio of structural units derived from each is preferably the same ratio as mentioned 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、トリフェニルホスフィン等）及び重合禁止剤（例えばハイドロキノン、メトキノン等）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。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［Ｋ４］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。
　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, part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the copolymer is reacted with the cyclic ether having 2 to 4 carbon atoms of (b).
Following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b) a reaction catalyst (e.g., tris ( Dimethylaminomethyl)phenol, triphenylphosphine, etc.) and a polymerization inhibitor (e.g., hydroquinone, metoquinone, etc.) are placed in a flask and reacted at, for example, 60 to 130 ° C. for 1 to 10 hours to obtain a resin [K4 ] can be manufactured.
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By setting it to this range, the storage stability of the colored curable composition, the developability when forming a pattern, and the solvent resistance, heat resistance, mechanical strength and sensitivity of the resulting pattern tend to have a good balance. There is Since the cyclic ether has high reactivity and unreacted (b) hardly remains, (b1) is preferable as the (b) used in the resin [K4], and (b1-1) is more preferable.
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 to be used is preferably 0.001 to 5 parts by weight per 100 parts by weight of the total amount of (a), (b) and (c).
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 polymerization, and the like. As with the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.
　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。 For resin [K5], as the first step, a copolymer of (b) and (c) is obtained in the same manner as in the method for producing resin [K1] described above. In the same manner as described above, the obtained copolymer may be used as a solution after the reaction as it is, may be used as a concentrated or diluted solution, or may be converted into a solid (powder) by a method such as reprecipitation. You may use what was taken out as.
The ratio of structural units derived from (b) and (c) to the total number of moles of all structural units constituting the copolymer is, respectively,
Structural unit derived from (b); 5 to 95 mol%
Structural unit derived from (c); 5 to 95 mol%
is preferably
Structural unit derived from (b); 10 to 90 mol%
Structural unit derived from (c); 10 to 90 mol%
is more preferable.
　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 method for producing resin [K4], the cyclic ether derived from (b) in the copolymer of (b) and (c) is added to the carboxylic acid or carboxylic anhydride of (a). Resin [K5] can be obtained by reacting substances.
The amount of (a) to be reacted with the copolymer is preferably 5 to 100 mol per 100 mol of (b). Since the cyclic ether has high reactivity and unreacted (b) does not easily remain, (b1) is preferable as (b) used in resin [K5], and (b1-1) is more preferable.
　樹脂［Ｋ６］は、樹脂［Ｋ５］に、さらにカルボン酸無水物を反応させた樹脂である。環状エーテルと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。
　カルボン酸無水物としては、無水コハク酸、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－エン無水物等が挙げられる。カルボン酸無水物の使用量は、（ａ）の使用量１モルに対して、０．１～１モルが好ましい。 Resin [K6] is a resin obtained by reacting resin [K5] with a carboxylic acid anhydride. The hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or carboxylic anhydride is reacted with the carboxylic anhydride.
Carboxylic anhydrides include succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, and 3,4,5,6-tetrahydrophthalic acid. anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride and the like. The amount of carboxylic acid anhydride to be used is preferably 0.1 to 1 mol per 1 mol of (a).
　具体的な樹脂（Ｂ）としては、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］；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／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／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／２－ヒドロキシエチル（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／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／グリシジル（メタ）アクリレート／ジシクロペンタニル（メタ）アクリレートの共重合体に（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。
　中でも、樹脂（Ｂ）としては、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種に由来する構造単位と、炭素数２～４の環状エーテル構造及びエチレン性不飽和結合を有する構造単位とを含む共重合体（樹脂［Ｋ１］又は樹脂［Ｋ２］）、又は樹脂［Ｋ６］が好ましい。 Specific resins (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] Resin [K1] such as decyl acrylate/(meth)acrylic acid copolymer; 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate/benzyl (meth)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/2-hydroxyethyl (meth)acrylate copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer, etc. resin [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymer, resin [K3] such as styrene / (meth) acrylic acid copolymer; benzyl (meth) acrylate / (meth) acrylic acid copolymer Resin obtained by adding glycidyl (meth)acrylate to polymer, resin obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, tricyclodecyl (meth) Resin [K4] such as resin obtained by adding glycidyl (meth)acrylate to acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer; copolymerization of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate Resins such as a resin obtained by reacting (meth)acrylic acid to a coalescence, a resin obtained by reacting (meth)acrylic acid to a copolymer of tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate [K5]; 2-Ethylhexyl (meth)acrylate/glycidyl resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid and further with tetrahydrophthalic anhydride. (meth)acrylate/dicyclopentanyl (meth)acrylate copolymer (meth) ) Resin [K6] such as a resin obtained by further reacting a resin obtained by reacting acrylic acid with succinic anhydride.
Among them, as the resin (B), a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, a cyclic ether structure having 2 to 4 carbon atoms and ethylenically unsaturated A copolymer containing a structural unit having a bond (resin [K1] or resin [K2]) or resin [K6] is preferred.
　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５００～１００，０００であり、より好ましくは６００～５０，０００であり、さらに好ましくは７００～３０，０００である。分子量が前記の範囲内にあると、カラー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。 The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 500 to 100,000, more preferably 600 to 50,000, still more preferably 700 to 30,000. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film rate is high, the solubility of the unexposed portion in the developing solution is good, and the resolution of the colored pattern tends to be improved.
　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 dispersion degree [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1-6, more preferably 1.2-4.
　樹脂（Ｂ）の酸価は、固形分換算で、好ましくは１０～１７０ｍｇ－ＫＯＨ／ｇであり、より好ましくは２０～１５０ｍｇ－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 the resin (B) is preferably 10-170 mg-KOH/g, more preferably 20-150 mg-KOH/g, still more preferably 30-135 mg-KOH/g, in terms of solid content. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be determined, for example, by titration using 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７～８０質量％であり、より好ましくは１３～７５質量％であり、さらに好ましくは１７～７０質量％、さらにより好ましくは１７～５５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 the resin (B) is preferably 7 to 80% by mass, more preferably 13 to 75% by mass, still more preferably 17 to 70% by mass, and even more preferably, relative to the total solid content. is 17 to 55% by mass. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the residual film rate tend to be improved.
＜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 an active radical and/or an acid generated from the polymerization initiator (D). is a (meth)acrylic acid ester compound.
　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、エチレンオキサイド変性ペンタエリスリトールテトラ（メタ）アクリレート、エチレンオキサイド変性ジペンタエリスリトールヘキサ（メタ）アクリレート、プロピレングリコール変性ペンタエリスリトールテトラ（メタ）アクリレート、プロピレングリコール変性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、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、及びエチレンオキサイド変性ジペンタエリスリトールヘキサ（メタ）アクリレートからなる群から選ばれる少なくとも１種が好ましい。 Among them, the polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa( meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl ) isocyanurate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like.
Among them, at least one selected from the group consisting of trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and ethylene oxide-modified dipentaerythritol hexa(meth)acrylate is preferred.
　重合性化合物（Ｃ）の重量平均分子量は、好ましくは１５０以上２，９００以下、より好ましくは２５０以上１，５００以下である。 The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 or more and 1,500 or less.
　重合性化合物（Ｃ）の含有率は、固形分の総量に対して、７～６５質量％であることが好ましく、より好ましくは１０～６０質量％であり、さらに好ましくは１２～５５質量％である。重合性化合物（Ｃ）の含有率が、前記の範囲内にあると、着色パターン形成時の残膜率及びカラーフィルタの耐薬品性が向上する傾向がある。 The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 10 to 60% by mass, still more preferably 12 to 55% by mass, based on the total solid content. be. When the content of the polymerizable compound (C) is within the above range, there is a tendency that the residual film ratio at the time of forming the colored pattern and the chemical resistance of the color filter are improved.
＜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る。本発明の着色硬化性組成物は、重合開始剤（Ｄ）としてオキシム化合物を含む。 <Polymerization initiator (D)>
The polymerization initiator (D) is a compound capable of initiating polymerization by generating active radicals, acids, etc. by the action of light or heat. The colored curable composition of the present invention contains an oxime compound as a polymerization initiator (D).
　前記オキシム化合物は、式（ｄ１）で表される部分構造を有するＯ－アシルオキシム化合物であることが好ましい。以下、＊は結合手を表す。 The oxime compound is preferably an O-acyl oxime compound having a partial structure represented by formula (d1). Below, * represents a bond.
Figure JPOXMLDOC01-appb-C000106
Figure JPOXMLDOC01-appb-C000106
　前記オキシム化合物としては、例えば、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）ブタン－１－オン－２－イミン、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）オクタン－１－オン－２－イミン、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）－３－シクロペンチルプロパン－１－オン－２－イミン、Ｎ－アセトキシ－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタン－１－イミン、Ｎ－アセトキシ－１－［９－エチル－６－｛２－メチル－４－（３，３－ジメチル－２，４－ジオキサシクロペンタニルメチルオキシ）ベンゾイル｝－９Ｈ－カルバゾール－３－イル］エタン－１－イミン、Ｎ－アセトキシ－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－３－シクロペンチルプロパン－１－イミン、Ｎ－ベンゾイルオキシ－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－３－シクロペンチルプロパン－１－オン－２－イミン、Ｎ－アセチルオキシ－１－［４－（２－ヒドロキシエチルオキシ）フェニルスルファニルフェニル］プロパン－１－オン－２－イミン、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、２－［（アセチルオキシ）イミノ］－３－シクロヘキシル－１－［４－（フェニルスルファニル）フェニル］プロパン－１－オン等が挙げられる。イルガキュアＯＸＥ０１、ＯＸＥ０２、ＯＸＥ０３（以上、ＢＡＳＦ製）、Ｎ－１９１９（ＡＤＥＫＡ製）、ＰＢＧ－３１４、ＰＢＧ－３１７、ＰＢＧ－３２６、ＰＢＧ－３２７、ＰＢＧ－３２９（以上、常州強力電子新材料（株）製）等の市販品を用いてもよい。中でも、オキシム化合物は、Ｎ－アセチルオキシ－１－［４－（２－ヒドロキシエチルオキシ）フェニルスルファニルフェニル］プロパン－１－オン－２－イミン、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、２－［（アセチルオキシ）イミノ］－３－シクロヘキシル－１－［４－（フェニルスルファニル）フェニル］プロパン－１－オン、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、２－［（アセチルオキシ）イミノ］－３－シクロヘキシル－１－［４－（フェニルスルファニル）フェニル］プロパン－１－オン、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、及び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。これらのオキシム化合物であると、高明度なカラーフィルタが得られる傾向にある。 Examples of the oxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1- On-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]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-di Oxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-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-(2-hydroxyethyloxy)phenylsulfanylphenyl]propan-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfanylphenyl) -3-cyclohexylpropan-1-one-2-imine, 2-[(acetyloxy)imino]-3-cyclohexyl-1-[4-(phenylsulfanyl)phenyl]propan-1-one and the like. Irgacure OXE01, OXE02, OXE03 (manufactured by BASF), N-1919 (manufactured by ADEKA), PBG-314, PBG-317, PBG-326, PBG-327, PBG-329 (manufactured by Changzhou Power Electronics New Materials Co., Ltd.) ) may be used. Among them, oxime compounds include N-acetyloxy-1-[4-(2-hydroxyethyloxy)phenylsulfanylphenyl]propan-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfanylphenyl )-3-cyclohexylpropan-1-one-2-imine, 2-[(acetyloxy)imino]-3-cyclohexyl-1-[4-(phenylsulfanyl)phenyl]propan-1-one, N-benzoyloxy -1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine and N-benzoyloxy-1 -(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine is preferably at least one selected from the group consisting of 2-[(acetyloxy)imino]-3-cyclohexyl-1-[ 4-(phenylsulfanyl)phenyl]propan-1-one, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, and N-acetyloxy-1-(4-phenyl At least one selected from the group consisting of sulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine is more preferred. These oxime compounds tend to give high-brightness color filters.
　また、本発明の着色硬化性組成物は、重合開始剤（Ｄ）としてオキシム化合物以外の他の重合開始剤を含んでいてもよく、他の重合開始剤としては、例えば、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及びビイミダゾール化合物等の活性ラジカルを発生する重合開始剤が挙げられる。 Further, the colored curable composition of the present invention may contain a polymerization initiator other than the oxime compound as the polymerization initiator (D). Examples of other polymerization initiators include alkylphenone compounds and triazines. polymerization initiators that generate active radicals such as compounds, acylphosphine oxide compounds and biimidazole compounds.
　前記アルキルフェノン化合物は、式（ｄ２）で表される部分構造又は式（ｄ３）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。 The alkylphenone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). In these partial structures, the benzene ring may have a substituent.
Figure JPOXMLDOC01-appb-C000107
Figure JPOXMLDOC01-appb-C000107
　式（ｄ２）で表される部分構造を有する化合物としては、例えば、２－メチル－２－モルホリノ－１－（４－メチルスルファニルフェニル）プロパン－１－オン、２－ジメチルアミノ－１－（４－モルホリノフェニル）－２－ベンジルブタン－１－オン、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］ブタン－１－オン等が挙げられる。イルガキュア３６９、９０７、３７９（以上、ＢＡＳＦ製）等の市販品を用いてもよい。 Examples of compounds having a partial structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4 -morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one etc. Commercially available products such as Irgacure 369, 907 and 379 (manufactured by BASF) may also be used.
　式（ｄ３）で表される部分構造を有する化合物としては、例えば、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、２－ヒドロキシ－２－メチル－１－〔４－（２－ヒドロキシエトキシ）フェニル〕プロパン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチル－１－（４－イソプロペニルフェニル）プロパン－１－オンのオリゴマー、α，α－ジエトキシアセトフェノン、ベンジルジメチルケタール等が挙げられる。
　感度の点で、アルキルフェノン化合物としては、式（ｄ２）で表される部分構造を有する化合物が好ましい。 Examples of compounds having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2 -hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxy Acetophenone, benzyl dimethyl ketal and the like can be mentioned.
From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (d2).
　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 compound 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-methoxy styryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4 -bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino- 2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc. is mentioned.
　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。 Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may 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。 Examples of the biimidazole compound include 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(alkoxyphenyl)biimidazole, 2,2′-bis (2-chlorophenyl)-4,4′,5,5′-tetra(dialkoxyphenyl)biimidazole, 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetra(tri alkoxyphenyl)biimidazole (see, for example, JP-B-48-38403, JP-A-62-174204, etc.), the phenyl group at the 4,4'5,5'-position being substituted with a carboalkoxy group; and biimidazole compounds (see, for example, JP-A-7-10913).
　さらに他の重合開始剤としては、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）（特にアミン化合物）と組み合わせて用いることが好ましい。 Further polymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4; Benzophenone compounds such as '-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2 -quinone compounds such as ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like. These are preferably used in combination with a polymerization initiation aid (D1) (particularly an amine compound) described later.
　また他の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の酸を発生する重合開始剤が挙げられる。 Other polymerization initiators include, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl Onium salts such as methylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylates , acid-generating polymerization initiators such as benzoin tosylate.
　重合開始剤（Ｄ）中、オキシム化合物の含有量は、５０質量％以上が好ましく、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、よりさらに好ましくは９５質量％以上、特に好ましくは９８質量％以上であり、１００質量％であってもよい。 The content of the oxime compound in the polymerization initiator (D) is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably It is 98% by mass or more, and may be 100% by mass.
　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０．１～３０質量部であり、より好ましくは１～２０質量部である。重合開始剤（Ｄ）の含有量が、前記の範囲内にあると、高感度化して露光時間が短縮される傾向があるためカラーフィルタの生産性が向上する。 The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). part by mass. 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 color filter.
＜重合開始助剤（Ｄ１）＞
　重合開始助剤（Ｄ１）は、重合開始剤によって重合が開始された重合性化合物の重合を促進するために用いられる化合物、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。
　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。 <Polymerization initiation aid (D1)>
The polymerization initiation aid (D1) is a compound or a sensitizer used to accelerate the polymerization of the polymerizable compound whose polymerization has been initiated by the polymerization initiator. When the polymerization initiation aid (D1) is included, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds and carboxylic acid compounds.
　前記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、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、中でも４，４’－ビス（ジエチルアミノ）ベンゾフェノンが好ましい。ＥＡＢ－Ｆ（保土谷化学工業（株）製）等の市販品を用いてもよい。 Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 -2-ethylhexyl dimethylaminobenzoate, N,N-dimethyl p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis (Ethylmethylamino)benzophenone and the like can be mentioned, and 4,4′-bis(diethylamino)benzophenone is particularly preferable. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may also be used.
　前記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、２－エチル－９，１０－ジブトキシアントラセン等が挙げられる。 Examples of the alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-di butoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene and the like.
　前記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、１－クロロ－４－プロポキシチオキサントン等が挙げられる。 Examples of the thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.
　前記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、ナフトキシ酢酸等が挙げられる。 Examples of the 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, naphthoxyacetic acid and the like.
　これらの重合開始助剤（Ｄ１）を用いる場合、その含有量は、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０．１～３０質量部、より好ましくは１～２０質量部である。重合開始助剤（Ｄ１）の量がこの範囲内にあると、さらに高感度で着色パターンを形成することができ、カラーフィルタの生産性が向上する傾向にある。 When using these polymerization initiation aids (D1), the content is preferably 0.1 to 30 parts by mass, with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is preferably 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of color filters tends to improve.
＜カルボナート化合物（Ｅ）＞
　カルボナート化合物（Ｅ）は、炭酸が有する２個の水素原子のうち、１つあるいは２つを置換基を有していてもよい炭化水素基で置換した化合物である。カルボナート化合物（Ｅ）としては、式（Ｉ）で表される化合物であることが好ましい。 <Carbonate compound (E)>
The carbonate compound (E) is a compound in which one or two of the two hydrogen atoms of carbonic acid are substituted with an optionally substituted hydrocarbon group. The carbonate compound (E) is preferably a compound represented by formula (I).
Figure JPOXMLDOC01-appb-C000108
 ［式（Ｉ）中、Ｒ1及びＲ2は、それぞれ独立して、置換基を有していてもよい炭素数１～２０の炭化水素基を表す。］
Figure JPOXMLDOC01-appb-C000108
 [In formula (I), R 1 and R 2 each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. ]
　Ｒ1及びＲ2で表される炭化水素基の炭素数は、４～２０であることが好ましく、より好ましくは４～１５、さらに好ましくは４～１０である。 The number of carbon atoms in the hydrocarbon group represented by R 1 and R 2 is preferably 4-20, more preferably 4-15, still more preferably 4-10.
　Ｒ1及びＲ2で表される炭素数１～２０の炭化水素基としては、Ｒa1～Ｒa14、Ｒb1～Ｒb3、Ｒx2、Ｒx4、Ｒx5、Ｒx11～Ｒx13、Ｒx15～Ｒx17、Ｒy1～Ｒy5、Ｒy11～Ｒy13及びＲy15～Ｒy17で表される炭化水素基として例示した基が挙げられ、直鎖状アルキル基、分枝鎖状アルキル基などの飽和脂肪族炭化水素基、アルケニル基、アルキニル基などの不飽和脂肪族炭化水素基、シクロアルキル基などの飽和脂環式炭化水素基、シクロアルケニル基などの不飽和脂環式炭化水素基、及び飽和又は不飽和多環式炭化水素基などの脂肪族炭化水素基；芳香族炭化水素基；並びにアラルキル基、アリールアルケニル基、１つ以上のフェニル基が結合したフェニル基などの上記炭化水素基を組み合わせた基などのいずれであってもよい。 Hydrocarbon groups having 1 to 20 carbon atoms represented by R 1 and R 2 include R a1 to R a14 , R b1 to R b3 , R x2 , R x4 , R x5 , R x11 to R x13 , R x15 to R x17 , R y1 to R y5 , R y11 to R y13 and R y15 to R y17 include the groups exemplified as the hydrocarbon groups, straight-chain alkyl groups, branched-chain alkyl groups and the like. saturated aliphatic hydrocarbon groups, alkenyl groups, unsaturated aliphatic hydrocarbon groups such as alkynyl groups, saturated alicyclic hydrocarbon groups such as cycloalkyl groups, unsaturated alicyclic hydrocarbon groups such as cycloalkenyl groups, and aliphatic hydrocarbon groups such as saturated or unsaturated polycyclic hydrocarbon groups; aromatic hydrocarbon groups; It may be any of a combination of groups and the like.
　Ｒ1及びＲ2で表される炭素数１～２０の炭化水素基は置換基を有していてもよく、該置換基としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、ニトロ基、シアノ基、－ＯＲxa1、－ＣＯ2Ｒxa1、－ＳＲxa1、－ＳＯ2Ｒxa1、－ＳＯ3Ｒxa1、－ＳＯ2ＮＲxa1Ｒxa2及び－ＮＲxa1Ｒxa2等が挙げられる（ただし、Ｒxa1及びＲxa2は前記に同じ）。 The hydrocarbon group having 1 to 20 carbon atoms represented by R 1 and R 2 may have a substituent, and the substituent may be a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. , nitro group, cyano group, —OR xa1 , —CO 2 R xa1 , —SR xa1 , —SO 2 R xa1 , —SO 3 R xa1 , —SO 2 NR xa1 R xa2 and —NR xa1 R xa2 and the like. (provided that R xa1 and R xa2 are the same as above).
　Ｒ1及びＲ2として、少なくとも一方が、置換基を有していてもよい炭素数１～２０の直鎖状又は分枝鎖状のアルキル基、置換基を有していてもよい炭素数６～２０の芳香族炭化水素基（以下、芳香族炭化水素基をアリール基という場合がある）、又は置換基を有していてもよい炭素数７～２０のアラルキル基であることが好ましい。
　またＲ1及びＲ2の両方が、それぞれ独立に、置換基を有していてもよい炭素数１～２０の直鎖状又は分枝鎖状のアルキル基、置換基を有していてもよい炭素数６～２０の芳香族炭化水素基、又は置換基を有していてもよい炭素数７～２０のアラルキル基であることがより好ましい。 At least one of R 1 and R 2 is an optionally substituted linear or branched C 1-20 alkyl group, or an optionally substituted C 6 It is preferably an aromatic hydrocarbon group of up to 20 (hereinafter, the aromatic hydrocarbon group may be referred to as an aryl group) or an optionally substituted aralkyl group of 7 to 20 carbon atoms.
Both R 1 and R 2 may independently have a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent or a substituent. It is more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms which may have a substituent.
　Ｒ1及びＲ2を表す前記炭素数１～２０の直鎖状又は分枝鎖状のアルキル基としては、炭素数４～２０の直鎖状又は分枝鎖状のアルキル基がより好ましく、炭素数４～２０の第二級又は第三級アルキル基がよりさらに好ましく、炭素数４～２０の第三級アルキル基が特に好ましい。 The linear or branched alkyl group having 1 to 20 carbon atoms representing R 1 and R 2 is more preferably a linear or branched alkyl group having 4 to 20 carbon atoms. A secondary or tertiary alkyl group having 4 to 20 carbon atoms is more preferred, and a tertiary alkyl group having 4 to 20 carbon atoms is particularly preferred.
　特に、Ｒ1及びＲ2の少なくとも一方が、置換基を有していてもよい炭素数４～２０の第三級アルキル基、置換基を有していてもよい炭素数６～２０のアリール基、又は置換基を有していてもよい炭素数７～２０のアラルキル基であることが好ましく、Ｒ1及びＲ2の両方が、それぞれ独立して、置換基を有していてもよい炭素数４～２０の第三級アルキル基、置換基を有していてもよい炭素数６～２０のアリール基、又は置換基を有していてもよい炭素数７～２０のアラルキル基であることがより好ましい。これらの好ましい態様において、前記第三級アルキル基は、ｔ－ブチル基であることが好ましく、前記炭素数６～２０のアリール基は、炭素数６～１０のアリール基であることが好ましく、フェニル基であることがさらに好ましく、前記炭素数７～２０のアラルキル基は、炭素数７～１０のアラルキル基であることが好ましく、ベンジル基であることがさらに好ましい。 In particular, at least one of R 1 and R 2 is an optionally substituted tertiary alkyl group having 4 to 20 carbon atoms and an optionally substituted aryl group having 6 to 20 carbon atoms. , or an optionally substituted aralkyl group having 7 to 20 carbon atoms, and both R 1 and R 2 each independently have an optionally substituted carbon number It is a 4-20 tertiary alkyl group, an optionally substituted C6-20 aryl group, or an optionally substituted C7-20 aralkyl group. more preferred. In these preferred embodiments, the tertiary alkyl group is preferably a t-butyl group, the aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 10 carbon atoms, phenyl and the aralkyl group having 7 to 20 carbon atoms is preferably an aralkyl group having 7 to 10 carbon atoms, more preferably a benzyl group.
　カルボナート化合物（Ｅ）の含有率は、固形分の総量に対して、例えば１質量％以上、好ましくは２質量％以上、より好ましくは３質量％以上であり、また例えば２０質量％以下、好ましくは１５質量％以下、より好ましくは１０質量％以下である。
　またカルボナート化合物（Ｅ）の量は、前記フタロシアニン化合物１００質量部に対して、好ましくは３質量部以上、より好ましくは５質量部以上であり、また４０質量部以下が好ましく、２５質量部以下がより好ましい。
　またカルボナート化合物（Ｅ）の量は、前記アルミフタロシアニン化合物１００質量部に対して、例えば２５質量部以上、好ましくは１００質量部以上、より好ましくは１５０質量部以上、さらに好ましくは１８０質量部以上であり、また例えば３５０質量部以下、好ましくは３００質量部以下、より好ましくは２５０質量部以下である。
　さらに、重合開始剤（Ｄ）に対するカルボナート化合物（Ｅ）の含有比（カルボナート化合物（Ｅ）／重合開始剤（Ｄ））は、例えば０．１以上、好ましくは０．２以上、より好ましくは０．５以上であり、また例えば１０以下、好ましくは８以下、より好ましくは５以下である。
　カルボナート化合物（Ｅ）の含有率が、前記の範囲内にあると、保存後であってもパターン安定性がより良好な着色硬化性組成物を提供できる。 The content of the carbonate compound (E) is, for example, 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and for example 20% by mass or less, preferably It is 15% by mass or less, more preferably 10% by mass or less.
The amount of the carbonate compound (E) is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, preferably 40 parts by mass or less, and 25 parts by mass or less, relative to 100 parts by mass of the phthalocyanine compound. more preferred.
The amount of the carbonate compound (E) is, for example, 25 parts by mass or more, preferably 100 parts by mass or more, more preferably 150 parts by mass or more, and still more preferably 180 parts by mass or more with respect to 100 parts by mass of the aluminum phthalocyanine compound. Also, for example, it is 350 parts by mass or less, preferably 300 parts by mass or less, more preferably 250 parts by mass or less.
Furthermore, the content ratio of the carbonate compound (E) to the polymerization initiator (D) (carbonate compound (E)/polymerization initiator (D)) is, for example, 0.1 or more, preferably 0.2 or more, more preferably 0 0.5 or more and, for example, 10 or less, preferably 8 or less, more preferably 5 or less.
When the content of the carbonate compound (E) is within the above range, it is possible to provide a colored curable composition with better pattern stability even after storage.
＜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。
　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。 <Leveling agent (F)>
Examples of the leveling agent (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymerizable group in the side chain.
Examples of silicone-based surfactants include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray SH7PA, Toray DC11PA, Toray SH21PA, Toray SH28PA, Toray SH29PA, Toray SH30PA, Toray SH8400 (trade name: Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, 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), etc. .
　前記の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）（旧旭硝子（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。 Examples of the fluorine-based surfactants include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, Florard FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Florado F171, Flora F172, Flora F173, Flora F177, Flora F183, Flora F554 R30, RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Examples include S382, SC101, SC105 (manufactured by AGC Co., Ltd. (former Asahi Glass Co., Ltd.)) and E5844 (manufactured by Daikin Fine Chemicals Laboratory Co., Ltd.).
　前記の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 the silicone-based surfactants having fluorine atoms include surfactants having siloxane bonds and fluorocarbon chains in the molecule. Specifically, Megafac (registered trademark) R08, Megafac BL20, Megafac F475, F477 and F443 (manufactured by DIC Corporation) and the like can be mentioned.
　レベリング剤（Ｆ）の含有率は、着色硬化性組成物の総量に対して、好ましくは０．００１～０．２質量％であり、より好ましくは０．００２～０．１質量％、さらに好ましくは０．００５～０．０５質量％である。尚、この含有率に、前記顔料分散剤の含有率は含まれない。レベリング剤（Ｆ）の含有率が前記の範囲内にあると、カラーフィルタの平坦性を良好にすることができる。 The content of the leveling agent (F) is preferably 0.001 to 0.2% by mass, more preferably 0.002 to 0.1% by mass, and still more preferably, relative to the total amount of the colored curable composition. is 0.005 to 0.05% by mass. 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 color filter can be improved.
＜溶剤（Ｇ）＞
　溶剤（Ｇ）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。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。 <Solvent (G)>
The solvent (G) is not particularly limited, and solvents commonly used in the field can be used. For example, ester solvent (solvent containing -COO- in the molecule but not containing -O-), ether solvent (solvent containing -O- in the molecule but not containing -COO-), ether ester solvent (solvent containing -COO- in the molecule solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O-, - solvents containing no CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.
　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－ブチロラクトンなどが挙げられる。 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 γ-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などが挙げられる。 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, and 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, phenetol and methylanisole and the like.
　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及びジエチレングリコールモノブチルエーテルアセテートなどが挙げられる。 Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl Ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like.
　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（ジアセトンアルコールという場合がある）、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などが挙げられる。 Ketone solvents include 4-hydroxy-4-methyl-2-pentanone (sometimes referred to as diacetone alcohol), acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone, isophorone, and the like.
　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などが挙げられる。 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、キシレン及びメシチレンなどが挙げられる。 　Aromatic hydrocarbon solvents include benzene, toluene, xylene and mesitylene.
　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－メチルピロリドンなどが挙げられる。 Amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.
　溶剤（Ｇ）は、エーテル溶剤、エーテルエステル溶剤及びアミド溶剤からなる群より選択される１種以上であることが好ましく、エーテル溶剤、エーテルエステル溶剤及びアミド溶剤を含むことがより好ましく、ジエチレングリコールメチルエチルエーテル、プロピレングリコールモノメチルエーテルアセテート、及びＮ－メチルピロリドンを含むことがさらに好ましい。
　また溶剤（Ｇ）は、エーテルエステル溶剤及びケトン溶剤からなる群より選択される１種以上を含むことが好ましい。 Solvent (G) is preferably one or more selected from the group consisting of ether solvents, ether ester solvents and amide solvents, more preferably includes ether solvents, ether ester solvents and amide solvents, diethylene glycol methyl ethyl More preferred are ethers, propylene glycol monomethyl ether acetate, and N-methylpyrrolidone.
Moreover, the solvent (G) preferably contains one or more selected from the group consisting of ether ester solvents and ketone solvents.
　また上記溶剤のうち、塗布性、乾燥性の点から、１ａｔｍにおける沸点が１２０℃以上１８０℃以下である有機溶剤が好ましい。このような溶剤としては、プロピレングリコールモノメチルエーテルアセテート、乳酸エチル、プロピレングリコールモノメチルエーテル、３－エトキシプロピオン酸エチル、エチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、４－ヒドロキシ－４－メチル－２－ペンタノン及びＮ，Ｎ－ジメチルホルムアミドからなる群から選択される少なくとも１種であることが好ましく、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、乳酸エチル、３－エトキシプロピオン酸エチル、及び４－ヒドロキシ－４－メチル－２－ペンタノンからなる群から選択される少なくとも１種であることがより好ましい。 Among the above solvents, organic solvents having a boiling point of 120° C. or higher and 180° C. or lower at 1 atm are preferable from the viewpoint of coating properties and drying properties. Such solvents include propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl- It is preferably at least one selected from the group consisting of 2-pentanone and N,N-dimethylformamide, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, and 4- More preferably, it is at least one selected from the group consisting of hydroxy-4-methyl-2-pentanone.
　溶剤（Ｇ）の含有率は、着色硬化性組成物の総量に対して、好ましくは７０～９５質量％であり、より好ましくは７５～９２質量％である。言い換えると、着色硬化性組成物の固形分は、好ましくは５～３０質量％、より好ましくは８～２５質量％である。溶剤（Ｇ）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、またカラーフィルタを形成した際に色濃度が不足しないために表示特性が良好となる傾向がある。 The content of the solvent (G) is preferably 70-95% by mass, more preferably 75-92% by mass, relative to the total amount of the colored curable composition. In other words, the solids content of the colored curable composition is preferably 5-30% by weight, more preferably 8-25% by weight. When the content of the solvent (G) is within the above range, the flatness at the time of coating is improved, and the display characteristics tend to be improved because the color density is not insufficient when a color filter is formed. .
＜その他の成分＞
　着色硬化性組成物は、必要に応じて、充填剤、他の高分子化合物、密着促進剤、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。 <Other ingredients>
The colored curable composition may optionally contain additives known in the art such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc. .
＜着色硬化性組成物の製造方法＞
　着色硬化性組成物は、例えば、フタロシアニン化合物を含む着色剤（Ａ）、樹脂（Ｂ）、重合性化合物（Ｃ）、重合開始剤（Ｄ）、及びカルボナート化合物（Ｅ）、並びに必要に応じて用いられる重合開始助剤（Ｄ１）、レベリング剤（Ｆ）、溶剤（Ｇ）、及びその他の成分を混合することにより調製できる。
　フタロシアニン化合物は、予め分散液に含ませてもよい。また、顔料を含む場合の顔料も、予め分散液に含ませてもよい。顔料を含む場合、フタロシアニン化合物と顔料は、１つの分散液として調製してもよいし、各々の分散液として調製してもよい。分散液に、残りの成分を、所定の濃度となるように混合することにより、目的の着色硬化性組成物を調製できる。
　染料を含む場合の染料は、予め溶剤（Ｇ）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。
　混合後の着色硬化性組成物を、孔径０．０１～１０μｍ程度のフィルタでろ過することが好ましい。 <Method for producing colored curable composition>
The colored curable composition includes, for example, a coloring agent (A) containing a phthalocyanine compound, a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a carbonate compound (E), and if necessary It can be prepared by mixing the polymerization initiation aid (D1), leveling agent (F), solvent (G) and other components used.
The phthalocyanine compound may be included in the dispersion in advance. In addition, when a pigment is included, the pigment may also be included in the dispersion in advance. When a pigment is included, the phthalocyanine compound and the pigment may be prepared as one dispersion or as separate dispersions. The desired colored curable composition can be prepared by mixing the remaining components with the dispersion liquid so as to have a predetermined concentration.
When a dye is contained, the dye may be dissolved in part or all of the solvent (G) in advance to prepare a solution. It is preferable to filter the solution through a filter having a pore size of about 0.01 to 1 μm.
It is preferable to filter the colored curable composition after mixing through a filter having a pore size of about 0.01 to 10 μm.
＜＜カラーフィルタ＞＞
　本発明の着色硬化性組成物からカラーフィルタの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、前記着色硬化性組成物を基板に塗布し、乾燥させて組成物層を形成し、フォトマスクを介して該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カラーフィルタである。 <<Color filter>>
Examples of the method for producing a colored pattern of a color filter from the colored curable composition of the present invention include a photolithography method, an inkjet method, a printing method and the like. Among them, the photolithographic method is preferred. Photolithography is a method in which the colored curable composition is applied to a substrate, dried to form a composition layer, exposed through a photomask, and developed. In the photolithographic method, a colored coating film, which is a cured product of the 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 color filter of the present invention.
　カラーフィルタ（着色塗膜）の膜厚は、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３μｍ以下、さらにより好ましくは１．５μｍ以下、特に好ましくは０．５μｍ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 color filter (colored coating film) is, for example, 30 μm or less, preferably 20 μm or less, more preferably 6 μm or less, even more preferably 3 μm or less, even more preferably 1.5 μm or less, and particularly preferably 0.5 μm or less. , preferably 0.1 μm or more, more preferably 0.2 μm or more, and still 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処理を施した基板を使用してもよい。 Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass whose surface is coated with silica; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; A thin film of aluminum, silver, silver/copper/palladium alloy, etc. is formed on the substrate. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates. Alternatively, a substrate obtained by subjecting a silicon substrate to HMDS processing may 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、３０～１２０℃が好ましく、５０～１１０℃がより好ましい。また加熱時間としては、１０秒間～６０分間であることが好ましく、３０秒間～３０分間であることがより好ましい。
　減圧乾燥を行う場合は、５０～１５０Ｐａの圧力下、２０～２５℃の温度範囲で行うことが好ましい。組成物層の膜厚は、特に限定されず、目的とするカラー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 the photolithographic method can be carried out using a known or commonly used apparatus and conditions. For example, it can be produced as follows.
First, a colored curable composition is applied onto a substrate, dried by heating (pre-baking) and/or dried under reduced pressure to remove volatile components such as solvents, and dried to obtain a smooth composition layer.
Examples of coating methods include a spin coating method, a slit coating method, a slit and spin coating method, and the like.
The temperature for heat drying is preferably 30 to 120°C, more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.
When drying under reduced pressure, it is preferably carried out at a pressure of 50 to 150 Pa and a temperature of 20 to 25°C. The film thickness of the composition layer is not particularly limited, and may be appropriately selected according to the desired film thickness of the color filter.
　次に、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。
　露光に用いられる光源としては、２５０～４５０ｎｍ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。
　露光面全体に均一に平行光線を照射したり、フォトマスクと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縮小投影露光装置またはプロキシミティ露光装置を使用することが好ましい。 The composition layer is then exposed through a photomask to form the desired colored pattern. The pattern on the photomask is not particularly limited, and a pattern suitable for the intended use is used.
The light source used for exposure is preferably a light source that emits light with a wavelength of 250 to 450 nm. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. You can Specifically, mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, and the like can be used.
Since it is possible to uniformly irradiate the entire exposure surface with parallel light rays and to perform accurate alignment between the photomask and the substrate, it is possible to use a reduction projection exposure apparatus such as a mask aligner and a stepper, or a proximity exposure apparatus. preferable.
　露光後の組成物層を現像液に接触させて現像することにより、基板上に着色パターンが形成される。現像により、組成物層の未露光部が現像液に溶解して除去される。現像液としては、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０．０１～１０質量％であり、より好ましくは０．０３～５質量％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。
　現像後は、水洗することが好ましい。 A colored pattern is formed on the substrate by developing the exposed composition layer in contact with a developer. By development, the unexposed portion of the composition layer is dissolved in the developer and removed. As the developer, for example, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate and tetramethylammonium hydroxide are preferred. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Furthermore, the developer may contain a surfactant. The developing method may be any of a puddle method, a dipping method, a spray method, and the like. Furthermore, the substrate may be tilted at any angle during development.
It is preferable to wash with water after development.
　さらに、得られた着色パターンに、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、８０～２５０℃が好ましく、１００～２４５℃がより好ましい。ポストベーク時間は、１～１２０分間が好ましく、２～３０分間がより好ましい。 Furthermore, it is preferable to post-bake the obtained colored pattern. The post-baking temperature is preferably 80 to 250°C, more preferably 100 to 245°C. Post-baking time is preferably 1 to 120 minutes, more preferably 2 to 30 minutes.
　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り、該カラーフィルタは、表示装置（例えば、液晶表示装置、有機ＥＬ表示装置等）、電子ペーパー、固体撮像素子等に用いられるカラーフィルタとして有用である。 The colored pattern and colored coating film thus obtained are useful as a color filter, and the color filter can be used for display devices (e.g., liquid crystal display devices, organic EL display devices, etc.), electronic paper, solid-state imaging devices, and the like. It is useful as a color filter used for
　以下、実施例を挙げて本発明をより詳細に説明するが、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い。例中、特に断りのない限り、「部」は「質量部」を、「％」は「質量％」を意味する。 Although the present invention will be described in more detail below with reference to examples, the present invention is not limited by the following examples. In the examples, "parts" means "parts by mass" and "%" means "% by mass" unless otherwise specified.
（合成例１）
　特許出願公開番号２０１６－７５８３７の段落０１８５の手法で下記式（ｘ１）で表される化合物（以下、化合物（ｘ１））を得た。 (Synthesis example 1)
A compound represented by the following formula (x1) (hereinafter referred to as compound (x1)) was obtained by the method of paragraph 0185 of Patent Application Publication No. 2016-75837.
Figure JPOXMLDOC01-appb-C000109
Figure JPOXMLDOC01-appb-C000109
（合成例２）
　特許出願公開番号２０１６－７５８３７に記載の手法で、下記式（ｘ２）で表される化合物（以下、化合物（ｘ２））を得た。 (Synthesis example 2)
A compound represented by the following formula (x2) (hereinafter referred to as compound (x2)) was obtained by the method described in Patent Application Publication No. 2016-75837.
Figure JPOXMLDOC01-appb-C000110
Figure JPOXMLDOC01-appb-C000110
（樹脂合成例１）
　還流冷却器、滴下ロート及び撹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、撹拌しながら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。重合開始剤含有溶液の滴下終了後、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１３７ｍＰａ・ｓ、固形分３６．８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ポリスチレン換算の重量平均分子量は１．０×１０3、分散度は１．９７、固形分換算の酸価は１１１ｍｇ－ＫＯＨ／ｇであった。樹脂（Ｂ－１）は、以下の構造単位を有する。 (Resin synthesis example 1)
A suitable amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, 340 parts of propylene glycol monomethyl ether acetate was added, and the flask was heated to 80°C while stirring. Then, 57 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2, 6 ] A mixed solution of 54 parts of a mixture of decan-9-yl acrylate (content ratio is 1:1 in terms of molar ratio), 239 parts of benzyl methacrylate and 73 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a solution prepared by dissolving 40 parts of a polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) in 197 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the completion of dropping the polymerization initiator-containing solution, it was held at 80 ° C. for 3 hours, cooled to room temperature, and measured with a Brookfield viscometer (23 ° C.). A polymer (resin (B-1)) solution was obtained. The resulting copolymer had a polystyrene-equivalent weight-average molecular weight of 1.0×10 3 , a dispersity of 1.97, and an acid value of 111 mg-KOH/g in terms of solid content. Resin (B-1) has the following structural units.
Figure JPOXMLDOC01-appb-C000111
Figure JPOXMLDOC01-appb-C000111
（樹脂合成例２）
　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ｔ－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。 (Resin synthesis example 2)
276.8 parts of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas inlet tube, and the mixture was stirred while being replaced with nitrogen and heated to 120°C. Then, to 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, 35.3 parts of t-butyl peroxy-2-ethylhexanoate (Polymerization initiator) was added dropwise into the flask from the dropping funnel over 2 hours. After completion of the dropwise addition, the mixture was further stirred at 120° C. for 30 minutes to carry out a copolymerization reaction to produce an addition copolymer. Thereafter, the inside of 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 introduced into the above addition copolymer solution. The reaction was continued at 110° C. for 10 hours to cleave the epoxy group and introduce a polymerizable unsaturated bond into the side chain of the polymer at the same time as the reaction between the epoxy group derived from glycidyl methacrylate and acrylic acid. Next, 24.2 parts of succinic anhydride was added to the reaction system, and the reaction was continued at 110°C for 1 hour to react the hydroxy groups generated by the cleavage of the epoxy groups with succinic anhydride to introduce carboxyl groups into the side chains. , to obtain the polymer. Finally, 383.3 parts of propylene glycol monomethyl ether acetate was added to the reaction solution to obtain a polymer (resin (B-2)) solution with a polymer solid content of 40%. The resulting copolymer (polymer; resin (B-2)) had a weight average molecular weight Mw of 6.3×10 3 and an acid value converted to solid content of 34 mg-KOH/g.
（分散液１の作製）
　Ｃ．Ｉ．ピグメントブルー１５：４を１２．０部、分散剤（ＢＹＫ社製　ＢＹＫＬＰＮ－６９１９）を３．６部、樹脂（Ｂ－１）（固形分換算）を５．４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７９部を混合し、０．４ｍｍのジルコニアビーズ３００部を加え、ペイントコンディショナー（ＬＡＵ社製）を使用して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分散液１を得た。 (Preparation of Dispersion 1)
C. I. Pigment Blue 15: 12.0 parts of 4, 3.6 parts of dispersant (BYKLPN-6919 manufactured by BYK), 5.4 parts of resin (B-1) (solid content conversion), propylene glycol monomethyl ether acetate 79 The parts were mixed and 300 parts of 0.4 mm zirconia beads were added and shaken for 1 hour using paint conditioner (manufactured by LAU). After that, the zirconia beads were removed by filtration to obtain Dispersion Liquid 1.
（分散液２の作製）
　化合物（ｘ１）を５．０部、分散剤（ＢＹＫ社製　ＢＹＫＬＰＮ－６９１９）を４．０部、樹脂（Ｂ－１）（固形分換算）を４．０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８７部を混合し、０．４ｍｍのジルコニアビーズ３００部を加え、ペイントコンディショナー（ＬＡＵ社製）を使用して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分散液２を得た。 (Preparation of dispersion liquid 2)
5.0 parts of the compound (x1), 4.0 parts of the dispersant (BYKLPN-6919 manufactured by BYK), 4.0 parts of the resin (B-1) (in terms of solid content), 87 parts of propylene glycol monomethyl ether acetate was mixed, 300 parts of 0.4 mm zirconia beads were added and shaken for 1 hour using a paint conditioner (manufactured by LAU). After that, the zirconia beads were removed by filtration to obtain Dispersion Liquid 2.
（分散液３の作製）
　Ｃ．Ｉ．ピグメントグリーン５８を１５部、分散剤（ＢＹＫ社製　ＢＹＫＬＰＮ－６９１９）を３．０部、樹脂（Ｂ－１）（固形分換算）を３．８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７８部を混合し、０．４ｍｍのジルコニアビーズ３００部を加え、ペイントコンディショナー（ＬＡＵ社製）を使用して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分散液３を得た。 (Preparation of dispersion liquid 3)
C. I. 15 parts of Pigment Green 58, 3.0 parts of dispersant (BYKLPN-6919 manufactured by BYK), 3.8 parts of resin (B-1) (in terms of solid content), and 78 parts of propylene glycol monomethyl ether acetate were mixed. , 300 parts of 0.4 mm zirconia beads were added and shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to obtain Dispersion Liquid 3.
（分散液４の作製）
　化合物（ｘ２）を５．０部、分散剤（ＢＹＫ社製　ＢＹＫＬＰＮ－６９１９）を４．０部、樹脂（Ｂ－１）（固形分換算）を４．０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８７部を混合し、０．４ｍｍのジルコニアビーズ３００部を加え、ペイントコンディショナー（ＬＡＵ社製）を使用して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分散液４を得た。 (Preparation of dispersion liquid 4)
5.0 parts of the compound (x2), 4.0 parts of the dispersant (BYKLPN-6919 manufactured by BYK), 4.0 parts of the resin (B-1) (in terms of solid content), 87 parts of propylene glycol monomethyl ether acetate was mixed, 300 parts of 0.4 mm zirconia beads were added and shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to obtain Dispersion Liquid 4.
〔実施例１～６、比較例１〕
（着色硬化性組成物の調製）
　表３６に示す成分を混合して、各々の着色硬化性組成物を得た。 [Examples 1 to 6, Comparative Example 1]
(Preparation of colored curable composition)
The components shown in Table 36 were mixed to obtain each colored curable composition.
Figure JPOXMLDOC01-appb-T000112
Figure JPOXMLDOC01-appb-T000112
　表３６において、各成分は以下のとおりである。
　　着色剤（Ａ－１）：分散液１
　　着色剤（Ａ－２）：分散液２
　　着色剤（Ａ－３）：分散液３
　　着色剤（Ａ－４）：分散液４
　　樹脂（Ｂ－２）：樹脂（Ｂ－２）（固形分換算）
　　重合性化合物（Ｃ－１）：エチレンオキサイド変性ジペンタエリスリトールヘキサアクリレート（新中村化学工業（株）製「Ａ－ＤＰＨ１２Ｅ」、エチレンオキサイド鎖の数：６、固形分換算）
　　重合開始剤（Ｄ－１）：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（常州強力電子新材料社製「ＴＲ－ＰＢＧ３２７」）
　　カルボナート化合物（Ｅ－１）：ｔｅｒｔ－Ｂｕｔｙｌ　Ｐｈｅｎｙｌ　Ｃａｒｂｏｎａｔｅ　東京化成工業（株）製（固形分換算）
　　カルボナート化合物（Ｅ－２）：Ｄｉｂｅｎｚｙｌ　Ｃａｒｂｏｎａｔｅ　東京化成工業（株）製（固形分換算）
　　レベリング剤（Ｆ－１）：ポリエーテル変性シリコーンオイル：商品名トーレシリコーンＳＨ８４００：東レダウコーニング（株）製（固形分換算）
　　溶剤（Ｇ－１）：ジアセトンアルコール
　　溶剤（Ｇ－２）：プロピレングリコールモノメチルエーテルアセテート In Table 36, each component is as follows.
Colorant (A-1): Dispersion 1
Colorant (A-2): Dispersion 2
Colorant (A-3): Dispersion 3
Colorant (A-4): Dispersion 4
Resin (B-2): Resin (B-2) (solid content conversion)
Polymerizable compound (C-1): ethylene oxide-modified dipentaerythritol hexaacrylate (“A-DPH12E” manufactured by Shin-Nakamura Chemical Co., Ltd., number of ethylene oxide chains: 6, converted to solid content)
Polymerization initiator (D-1): N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine (“TR-PBG327” manufactured by Changzhou Tenryu Electric New Materials Co., Ltd.)
Carbonate compound (E-1): tert-Butyl Phenyl Carbonate manufactured by Tokyo Chemical Industry Co., Ltd. (solid content conversion)
Carbonate compound (E-2): Dibenzyl Carbonate manufactured by Tokyo Chemical Industry Co., Ltd. (solid content conversion)
Leveling agent (F-1): Polyether-modified silicone oil: Trade name Toray Silicone SH8400: manufactured by Dow Corning Toray Co., Ltd. (solid content conversion)
Solvent (G-1): diacetone alcohol Solvent (G-2): propylene glycol monomethyl ether acetate
（着色パターンの作製）
　４インチのシリコン基板上に、各実施例および比較例の着色硬化性組成物をポストベーク後の膜厚が０．８μｍになるように各々スピンコート法で塗布した後、８０℃で２分間プリベークして着色組成物層を得た。冷却後、着色組成物層を形成した基板を露光機（ＮＳＲ－１７５５ｉ７Ａ；ニコン（株）製）を用いて、３００ｍＪ／ｃｍ2の露光量（３６５ｎｍ基準）で光照射した。フォトマスクとして、２．０μｍ四方のドットパターンが形成されたものを使用した。光照射後の着色組成物層を、テトラメチルアンモニウムヒドロキシドを含む水系現像液に２３℃で３０秒間浸漬現像し、水洗後、現像後（ポストベーク前）基板を２３０℃で１０分間ポストベークし、ポストベーク後の着色パターンＩを得た。
　また、実施例１、２および比較例１の着色硬化性組成物を４０℃で３日保管した後に、上記と同様の方法にてポストベーク後の着色パターンＩＩを得た。実施例３～６の着色硬化性組成物を４０℃で１日保管した後に、上記と同様の方法にてポストベーク後の着色パターンＩＩを得た。 (Preparation of colored pattern)
On a 4-inch silicon substrate, each of the colored curable compositions of Examples and Comparative Examples was applied by spin coating so that the film thickness after post-baking was 0.8 μm, and then pre-baked at 80° C. for 2 minutes. to obtain a colored composition layer. After cooling, the substrate on which the colored composition layer was formed was irradiated with light at an exposure amount of 300 mJ/cm 2 (365 nm standard) using an exposure machine (NSR-1755i7A; manufactured by Nikon Corporation). A photomask on which a 2.0 μm square dot pattern was formed was used. The colored composition layer after light irradiation is immersed in an aqueous developer containing tetramethylammonium hydroxide for 30 seconds at 23 ° C. After washing, the substrate after development (before post-baking) is post-baked at 230 ° C. for 10 minutes. , to obtain a colored pattern I after post-baking.
Further, after storing the colored curable compositions of Examples 1 and 2 and Comparative Example 1 at 40° C. for 3 days, post-baked colored patterns II were obtained in the same manner as described above. After storing the colored curable compositions of Examples 3 to 6 at 40° C. for one day, a post-baked colored pattern II was obtained in the same manner as described above.
（着色パターンの裾引き性評価）
　上記で得られた着色パターンＩ又は着色パターンＩＩを有するシリコンウェハ基板について、電子顕微鏡（Ｓ－４１００、日立ハイテク社製）を用いて、倍率３００００倍で形成された着色パターンを観察し下記式に基づいて線幅の変化率を評価した。結果を表３７に示す。線幅変化率が１（すなわち、１００％）に近い程、パターンの線幅の減少が抑制されているため好ましい。
　線幅変化率＝（着色パターンＩＩの線幅／着色パターンＩの線幅）×１００ (Evaluation of bottoming property of colored pattern)
For the silicon wafer substrate having colored pattern I or colored pattern II obtained above, an electron microscope (S-4100, manufactured by Hitachi High-Tech) was used to observe the colored pattern formed at a magnification of 30,000 times. The rate of change in line width was evaluated based on The results are shown in Table 37. The closer the line width change rate is to 1 (that is, 100%), the more suppressed the decrease in the line width of the pattern, which is preferable.
Line width change rate = (line width of colored pattern II/line width of colored pattern I) x 100
Figure JPOXMLDOC01-appb-T000113
Figure JPOXMLDOC01-appb-T000113
　カルボナート化合物を含まない比較例では、保存後の着色硬化性組成物を用いた場合、パターンが形成されなかった。一方カルボナート化合物を含む実施例では、保存後の着色硬化性組成物を用いた場合であっても、パターンの線幅の減少を抑制できた。 In the comparative example containing no carbonate compound, no pattern was formed when the colored curable composition after storage was used. On the other hand, in the examples containing the carbonate compound, even when the colored curable composition after storage was used, the decrease in the line width of the pattern could be suppressed.

Claims (9)

  1. 　着色剤、樹脂、重合性化合物、重合開始剤、及びカルボナート化合物を含有し、
    　前記着色剤が、フタロシアニン化合物を含み、
    　前記重合開始剤が、オキシム化合物を含む着色硬化性組成物。     containing a coloring agent, a resin, a polymerizable compound, a polymerization initiator, and a carbonate compound,
    the coloring agent comprises a phthalocyanine compound,
    The colored curable composition, wherein the polymerization initiator contains an oxime compound.
  2. 　前記カルボナート化合物が、式（Ｉ）で表される化合物である請求項１に記載の着色硬化性組成物。
    Figure JPOXMLDOC01-appb-C000001
     ［式（Ｉ）中、Ｒ1及びＲ2は、それぞれ独立して、置換基を有していてもよい炭素数１～２０の炭化水素基を表す。］     2. The colored curable composition according to claim 1, wherein the carbonate compound is a compound represented by formula (I).
    Figure JPOXMLDOC01-appb-C000001
     [In formula (I), R 1 and R 2 each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. ]
  3. 　前記Ｒ1及びＲ2の少なくとも一方が、置換基を有していてもよい炭素数４～２０の第三級アルキル基、置換基を有していてもよい炭素数６～２０のアリール基、又は置換基を有していてもよい炭素数７～２０のアラルキル基である請求項２に記載の着色硬化性組成物。 at least one of R 1 and R 2 is an optionally substituted tertiary alkyl group having 4 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, Or the colored curable composition according to claim 2, which is an optionally substituted aralkyl group having 7 to 20 carbon atoms.
  4. 　前記フタロシアニン化合物が、式（Ｘ１）～式（Ｘ３）で表される化合物のいずれかである請求項１に記載の着色硬化性組成物。
    Figure JPOXMLDOC01-appb-C000002
    Figure JPOXMLDOC01-appb-C000003
    Figure JPOXMLDOC01-appb-C000004
     ［式（Ｘ１）中、
    　Ｘx1～Ｘx4は、それぞれ独立に、－Ｒx4、－ＯＲx4、－ＳＲx4、－ＳＯ3Ｈ、－ＳＯ3 -Ｔ+、－ＳＯ3ＲX10、－ＳＯ2ＮＲX11ＲX12、ハロゲン原子、又はニトロ基を表す。
    　Ｒx4は、置換基を有していてもよい炭素数１～２０の炭化水素基を表し、該炭化水素基の炭素数が２～２０であり且つ該炭化水素基が－ＣＨ2－を有する場合、該－ＣＨ2－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わっていてもよい。
    　Ｔ+は、+Ｎ（ＲX13）4又はアルカリ金属イオンを表し、ＲX13は、それぞれ独立に、水素原子又は炭素数１～２０の炭化水素基を表す。
    　ＲX10は、炭素数１～２０の飽和炭化水素基を表す。
    　ＲX11及びＲX12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１～２０の炭化水素基を表す。
    　ｎｘ１～ｎｘ４は、それぞれ独立に、０～４の整数を表す。
    式（Ｘ２）中、
    　Ｍ1は、金属原子、金属酸化物、金属水酸化物、金属ハロゲン化物、リン含有基結合金属、ケイ素含有基結合金属、オキシカルボニル含有基結合金属、またはオキシスルホニル含有基結合金属を表す。
    　Ｘx1～Ｘx4及びｎｘ１～ｎｘ４は、前記に同じ。
    式（Ｘ３）中、
    　Ｍ2及びＭ3は、それぞれ独立に、金属原子、金属酸化物、金属水酸化物、または金属ハロゲン化物を表す。
    　Ｌは、－Ｏ－ＳｉＲa6Ｒa7－Ｏ－、－Ｏ－ＳｉＲa8Ｒa9－Ｏ－ＳｉＲa10Ｒa11－Ｏ－、または－Ｏ－Ｐ（＝Ｏ）Ｒa12－Ｏ－を表す。
    　Ｒa6～Ｒa12は、それぞれ独立に、水素原子、ヒドロキシ基、置換基を有していてもよい炭素数１～２０の炭化水素基、又は置換基を有していてもよい炭素数１～２０の複素環基を表し、Ｒa6とＲa7、Ｒa8とＲa9、またはＲa10とＲa11は、互いに結合して環を形成してもよい。該炭化水素基の炭素数が２～２０であり且つ該炭化水素基が－ＣＨ2－を有する場合、該－ＣＨ2－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わっていてもよい。
    　Ｘx5～Ｘx12は、それぞれ独立に、－Ｒx5、－ＯＲx5、－ＳＲx5、－ＳＯ3Ｈ、－ＳＯ3 -Ｑ+、－ＳＯ3ＲX14、－ＳＯ2ＮＲX15ＲX16、ハロゲン原子、又はニトロ基を表す。
    　Ｒx5は、置換基を有していてもよい炭素数１～２０の炭化水素基を表し、該炭化水素基の炭素数が２～２０であり且つ該炭化水素基が－ＣＨ2－を有する場合、該－ＣＨ2－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わっていてもよい。
    　Ｑ+は、+Ｎ（ＲX17）4又はアルカリ金属イオンを表し、ＲX17は、それぞれ独立に、水素原子又は炭素数１～２０の炭化水素基を表す。
    　ＲX14は、炭素数１～２０の飽和炭化水素基を表す。
    　ＲX15及びＲX16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１～２０の炭化水素基を表す。
    　ｎｘ５～ｎｘ１２は、それぞれ独立に、０～４の整数を表す。］     2. The colored curable composition according to claim 1, wherein the phthalocyanine compound is any one of compounds represented by formulas (X1) to (X3).
    Figure JPOXMLDOC01-appb-C000002
    Figure JPOXMLDOC01-appb-C000003
    Figure JPOXMLDOC01-appb-C000004
     [In the formula (X1),
    X x1 to X x4 each independently represent -R x4 , -OR x4 , -SR x4 , -SO 3 H, -SO 3 - T + , -SO 3 R x10 , -SO 2 NR x11 R x12 , halogen represents an atom or a nitro group.
    R x4 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group having 2 to 20 carbon atoms and having —CH 2 — In some cases, the --CH 2 -- may be replaced with --O--, --S-- or --CO--.
    T + represents + N(R X13 ) 4 or an alkali metal ion, and each R X13 independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
    R X10 represents a saturated hydrocarbon group having 1 to 20 carbon atoms.
    R X11 and R X12 each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
    nx1 to nx4 each independently represent an integer of 0 to 4;
    In formula (X2),
    M 1 represents a metal atom, a metal oxide, a metal hydroxide, a metal halide, a phosphorus-containing group-bonded metal, a silicon-containing group-bonded metal, an oxycarbonyl-containing group-bonded metal, or an oxysulfonyl-containing group-bonded metal.
    X x1 to X x4 and nx1 to nx4 are the same as above.
    In formula (X3),
    M 2 and M 3 each independently represent a metal atom, metal oxide, metal hydroxide, or metal halide.
    L represents -O-SiR a6 R a7 -O-, -O-SiR a8 R a9 -O-SiR a10 R a11 -O-, or -OP(=O)R a12 -O-.
    R a6 to R a12 each independently represent a hydrogen atom, a hydroxy group, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted C 1 to represents 20 heterocyclic groups, and R a6 and R a7 , R a8 and R a9 , or R a10 and R a11 may combine with each other to form a ring; When the hydrocarbon group has 2 to 20 carbon atoms and has —CH 2 —, the —CH 2 — may be replaced with —O—, —S— or —CO—. good.
    X x5 to X x12 each independently represent -R x5 , -OR x5 , -SR x5 , -SO 3 H, -SO 3 - Q + , -SO 3 R x14 , -SO 2 NR x15 R x16 , halogen represents an atom or a nitro group.
    R x5 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group having 2 to 20 carbon atoms, and the hydrocarbon group having —CH 2 — In some cases, the --CH 2 -- may be replaced with --O--, --S-- or --CO--.
    Q + represents + N(R X17 ) 4 or an alkali metal ion, and each R X17 independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
    R X14 represents a saturated hydrocarbon group having 1 to 20 carbon atoms.
    R X15 and R X16 each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
    nx5 to nx12 each independently represent an integer of 0 to 4; ]
  5. 　前記フタロシアニン化合物が、式（Ｘａ）又は式（Ｘｂ）で表される化合物である請求項１に記載の着色硬化性組成物。
    Figure JPOXMLDOC01-appb-C000005
    Figure JPOXMLDOC01-appb-C000006
     ［式（Ｘａ）中、
    　Ｚは、ヒドロキシ基、塩素原子、－ＯＰ（＝Ｏ）Ｒa1Ｒa2、－Ｏ－ＳｉＲa3Ｒa4Ｒa5、－ＯＣ（＝Ｏ）Ｒa13、又は－ＯＳ（＝Ｏ）2Ｒa14を表す。
    　Ｒa1～Ｒa5、及びＲa13～Ｒa14は、それぞれ独立に、水素原子、ヒドロキシ基、置換基を有していてもよい炭素数１～２０の炭化水素基、又は置換基を有していてもよい炭素数１～２０の複素環基を表し、Ｒa1とＲa2、またはＲa3～Ｒa5のいずれか二つは、互いに結合して環を形成してもよい。該炭化水素基の炭素数が２～２０であり且つ該炭化水素基が－ＣＨ2－を有する場合、該－ＣＨ2－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わっていてもよい。
    　Ｘx1～Ｘx4は、それぞれ独立に、－Ｒx4、－ＯＲx4、－ＳＲx4、－ＳＯ3Ｈ、－ＳＯ3 -Ｔ+、－ＳＯ3ＲX10、－ＳＯ2ＮＲX11ＲX12、ハロゲン原子、又はニトロ基を表す。
    　Ｒx4は、置換基を有していてもよい炭素数１～２０の炭化水素基を表し、該炭化水素基の炭素数が２～２０であり且つ該炭化水素基が－ＣＨ2－を有する場合、該－ＣＨ2－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わっていてもよい。
    　Ｔ+は、+Ｎ（ＲX13）4又はアルカリ金属イオンを表し、ＲX13は、それぞれ独立に、水素原子又は炭素数１～２０の炭化水素基を表す。
    　ＲX10は、炭素数１～２０の飽和炭化水素基を表す。
    　ＲX11及びＲX12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１～２０の炭化水素基を表す。
    　ｎｘ１～ｎｘ４は、それぞれ独立に、０～４の整数を表す。
    式（Ｘｂ）中、
    　Ｌは、－Ｏ－ＳｉＲa6Ｒa7－Ｏ－、－Ｏ－ＳｉＲa8Ｒa9－Ｏ－ＳｉＲa10Ｒa11－Ｏ－、または－Ｏ－Ｐ（＝Ｏ）Ｒa12－Ｏ－を表す。
    　Ｒa6～Ｒa12は、それぞれ独立に、水素原子、ヒドロキシ基、置換基を有していてもよい炭素数１～２０の炭化水素基、又は置換基を有していてもよい炭素数１～２０の複素環基を表し、Ｒa6とＲa7、Ｒa8とＲa9、またはＲa10とＲa11は、互いに結合して環を形成してもよい。該炭化水素基の炭素数が２～２０であり且つ該炭化水素基が－ＣＨ2－を有する場合、該－ＣＨ2－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わっていてもよい。
    　Ｘx5～Ｘx12は、それぞれ独立に、－Ｒx5、－ＯＲx5、－ＳＲx5、－ＳＯ3Ｈ、－ＳＯ3 -Ｑ+、－ＳＯ3ＲX14、－ＳＯ2ＮＲX15ＲX16、ハロゲン原子、又はニトロ基を表す。
    　Ｒx5は、置換基を有していてもよい炭素数１～２０の炭化水素基を表し、該炭化水素基の炭素数が２～２０であり且つ該炭化水素基が－ＣＨ2－を有する場合、該－ＣＨ2－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わっていてもよい。
    　Ｑ+は、+Ｎ（ＲX17）4又はアルカリ金属イオンを表し、ＲX17は、それぞれ独立に、水素原子又は炭素数１～２０の炭化水素基を表す。
    　ＲX14は、炭素数１～２０の飽和炭化水素基を表す。
    　ＲX15及びＲX16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１～２０の炭化水素基を表す。
    　ｎｘ５～ｎｘ１２は、それぞれ独立に、０～４の整数を表す。］     2. The colored curable composition according to claim 1, wherein the phthalocyanine compound is a compound represented by formula (Xa) or formula (Xb).
    Figure JPOXMLDOC01-appb-C000005
    Figure JPOXMLDOC01-appb-C000006
     [in the formula (Xa),
    Z is a hydroxy group, a chlorine atom, -OP(=O)R a1 R a2 , -O-SiR a3 R a4 R a5 , -OC(=O) R a13 or -OS(=O) 2 R a14 show.
    R a1 to R a5 and R a13 to R a14 each independently have a hydrogen atom, a hydroxy group, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. any two of R a1 and R a2 or R a3 to R a5 may combine with each other to form a ring. When the hydrocarbon group has 2 to 20 carbon atoms and has —CH 2 —, the —CH 2 — may be replaced with —O—, —S— or —CO—. good.
    X x1 to X x4 each independently represent -R x4 , -OR x4 , -SR x4 , -SO 3 H, -SO 3 - T + , -SO 3 R x10 , -SO 2 NR x11 R x12 , halogen represents an atom or a nitro group.
    R x4 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group having 2 to 20 carbon atoms and having —CH 2 — In some cases, the --CH 2 -- may be replaced with --O--, --S-- or --CO--.
    T + represents + N(R X13 ) 4 or an alkali metal ion, and each R X13 independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
    R X10 represents a saturated hydrocarbon group having 1 to 20 carbon atoms.
    R X11 and R X12 each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
    nx1 to nx4 each independently represent an integer of 0 to 4;
    In formula (Xb),
    L represents -O-SiR a6 R a7 -O-, -O-SiR a8 R a9 -O-SiR a10 R a11 -O-, or -OP(=O)R a12 -O-.
    R a6 to R a12 each independently represent a hydrogen atom, a hydroxy group, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted C 1 to represents 20 heterocyclic groups, and R a6 and R a7 , R a8 and R a9 , or R a10 and R a11 may combine with each other to form a ring; When the hydrocarbon group has 2 to 20 carbon atoms and has —CH 2 —, the —CH 2 — may be replaced with —O—, —S— or —CO—. good.
    X x5 to X x12 each independently represent -R x5 , -OR x5 , -SR x5 , -SO 3 H, -SO 3 - Q + , -SO 3 R x14 , -SO 2 NR x15 R x16 , halogen represents an atom or a nitro group.
    R x5 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group having 2 to 20 carbon atoms, and the hydrocarbon group having —CH 2 — In some cases, the --CH 2 -- may be replaced with --O--, --S-- or --CO--.
    Q + represents + N(R X17 ) 4 or an alkali metal ion, and each R X17 independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
    R X14 represents a saturated hydrocarbon group having 1 to 20 carbon atoms.
    R X15 and R X16 each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
    nx5 to nx12 each independently represent an integer of 0 to 4; ]
  6. 　前記式（Ｘａ）で表される化合物が式（Ｘ０）又は式（ＸＩ）で表される化合物であり、式（Ｘｂ）で表される化合物が式（ＸＩＩ）で表される化合物である請求項５に記載の着色硬化性組成物。
    Figure JPOXMLDOC01-appb-C000007
    Figure JPOXMLDOC01-appb-C000008
    Figure JPOXMLDOC01-appb-C000009
     ［式（ＸＩ）中、
    　Ｒx1は、置換基を有していてもよい炭素数２～２０の脂肪族不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の芳香族炭化水素基を表し、Ｒx2は、水素原子、置換基を有していてもよい炭素数１～２０の炭化水素基、又はＺx2とＲx1とを結ぶ単結合を表す。
    　Ｚx1及びＺx2は、それぞれ独立に、単結合又は酸素原子を表す。
    式（Ｘ０）及び式（ＸＩ）中、
    　Ｘx1～Ｘx4、ｎｘ１～ｎｘ４は、前記に同じ。
    式（ＸＩＩ）中、
    　Ｒx3は、置換基を有していてもよい炭素数２～２０の脂肪族不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の芳香族炭化水素基を表す。
    　Ｚx3は、単結合又は酸素原子を表す。
    　Ｘx5～Ｘx12、ｎｘ５～ｎｘ１２は、前記に同じ。］     wherein the compound represented by formula (Xa) is a compound represented by formula (X0) or formula (XI), and the compound represented by formula (Xb) is a compound represented by formula (XII) Item 6. The colored curable composition according to item 5.
    Figure JPOXMLDOC01-appb-C000007
    Figure JPOXMLDOC01-appb-C000008
    Figure JPOXMLDOC01-appb-C000009
     [in the formula (XI),
    R x1 represents an optionally substituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, R x2 represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or a single bond connecting Z x2 and R x1 .
    Z x1 and Z x2 each independently represent a single bond or an oxygen atom.
    In formula (X0) and formula (XI),
    X x1 to X x4 and nx1 to nx4 are the same as above.
    In formula (XII),
    R x3 represents an optionally substituted C 2-20 aliphatic unsaturated hydrocarbon group or an optionally substituted C 6-20 aromatic hydrocarbon group.
    Z x3 represents a single bond or an oxygen atom.
    X x5 to X x12 and nx5 to nx12 are the same as above. ]
  7. 　請求項１～６のいずれかに記載の着色硬化性組成物から形成されるカラーフィルタ。 A color filter formed from the colored curable composition according to any one of claims 1 to 6.
  8. 　請求項７に記載のカラーフィルタを含む表示装置。 A display device including the color filter according to claim 7.
  9. 　請求項７に記載のカラーフィルタを含む固体撮像素子。 A solid-state imaging device including the color filter according to claim 7.
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