JP6672725B2 - Colored curable resin composition - Google Patents

Description

  The present invention relates to a colored curable resin composition.

  The colored curable resin composition is used for producing a color filter used for a display device such as a liquid crystal display device, an electroluminescence display device, and a plasma display. As such a colored curable resin composition, a xanthene dye and a C.I. I. A pigmented curable resin composition containing only Pigment Blue 15: 6 is known (Patent Document 1).

JP 2010-21198 A

  An object of the present invention is to provide a colored curable resin composition in which a residue hardly occurs during development in the production of a color filter.

The present invention includes the following inventions.
[1] containing a colorant, a resin, a polymerizable compound and a polymerization initiator,
The coloring agent is a coloring agent containing a xanthene dye, a cyanine dye, and a blue pigment, or a coloring curable resin that is a coloring agent containing a salt of an anion derived from a xanthene compound and a cation derived from a cyanine compound and a coloring agent containing a blue pigment. Composition.
[2] The colored curable resin composition according to [1], wherein the polymerization initiator is a polymerization initiator containing at least one compound selected from the group consisting of an oxime compound, an alkylphenone compound, and a biimidazole compound.
[3] The colored curable resin composition according to [1] or [2], wherein the polymerization initiator is a polymerization initiator containing an oxime compound.
[4] Further, a blue or violet dye, which is different from each dye of xanthene dye and cyanine dye, and includes a dye different from a salt of an anion derived from a xanthene compound and a cation derived from a cyanine compound [1] ] The colored curable resin composition of any one of [3].
[5] A color filter formed from the colored curable resin composition according to any one of [1] to [4].
[6] A display device including the color filter according to [5].

  ADVANTAGE OF THE INVENTION According to the colored curable resin composition of this invention, the development residue can be reduced at the time of a color filter manufacture.

The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). The colorant (A) is a colorant containing a xanthene dye (A1), a cyanine dye (A2) and a blue pigment, or a salt of an anion derived from a xanthene compound and a cation derived from a cyanine compound, and a blue pigment. including.
The colored curable resin composition of the present invention preferably further contains a solvent (F).
It is preferable that the colored curable resin composition of the present invention further contains at least one selected from an antioxidant and a thiol compound.
It is preferable that the colored curable resin composition of the present invention further contains a leveling agent (G).
The colored curable resin composition of the present invention may contain a polymerization initiator (E).
In the present specification, compounds exemplified as each component can be used alone or in combination of two or more kinds, unless otherwise specified.

<Colorant (A)>
The colorant (A) contains a xanthene dye (A1), a cyanine dye (A2), and a blue pigment, or contains a salt of an anion derived from a xanthene compound and a cation derived from a cyanine compound, and a blue pigment.
The colorant (A) is a colorant comprising a xanthene dye (A1), a cyanine dye (A2) and a blue pigment, or a colorant comprising a salt of an anion derived from a xanthene compound and a cation derived from a cyanine compound and a blue pigment. It may be an agent.
The colorant (A) further includes a blue or violet dye (hereinafter, sometimes referred to as dye (A4)) different from each of the xanthene dye (A1) and the cyanine dye (A2), and other pigments (A3). ), And preferably contains a dye (A4).

  The xanthene dye is a dye containing only a compound having a xanthene skeleton in a molecule (hereinafter, sometimes referred to as a xanthene compound) as a dye. Xanthene dyes include, for example, C.I. I. Acid Red 50 (hereinafter, description of CI Acid Red is omitted, and only the number is described. Others are the same), 51, 52, 87, 91, 92, 94, 289, 388, C . I. Acid violet 9, 30, 102, C.I. I. Basic Red 1 (rhodamine 6G), 2, 3, 4, 8, C.I. I. Basic Red 10, 11, C.I. I. Basic violet 10 (rhodamine B), 11, C.I. I. Solvent Red 218, C.I. I. Modern Red 27, C.I. I. Reactive Red 36 (rose bengal B), sulforhodamine G, xanthene dyes described in JP-A-2010-32999, and xanthene dyes described in JP-A-4492760. As the xanthene dye (A1), a dye soluble in an organic solvent is preferable.

The xanthene dye (A1) is preferably a dye containing a compound represented by the formula (1a) (hereinafter, may be referred to as “compound (1a)”). Compound (1a) may be a tautomer thereof.
When the xanthene dye (A1) contains the compound (1a), the content of the compound (1a) in the xanthene dye (A1) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass. % Or more. In particular, the xanthene dye (A1) preferably contains only the compound (1a).

[In the formula (1a), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or substituted monovalent aromatic hydrocarbon group having carbon atoms which may 6 to 10, _-CH 2 contained in the saturated hydrocarbon group - is, -O -, - CO- or -NR ^{11 -} may be replaced by. R ¹ and R ² may bond together to form a ring containing a nitrogen atom, and R ³ and R ⁴ may bond together to form a ring containing a nitrogen atom.
R ^{5 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ represents NR ⁹ R ¹⁰ .
R ⁶ and R ⁷ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 5. When m is 2 or more, a plurality of R ⁵ may be the same or different.
a represents an integer of 0 or 1.
X ^- represents a halide ion.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and the four R ¹¹ may be the same or different.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and is included in the saturated aliphatic hydrocarbon group. CH ₂ — may be replaced by —O—, —CO—, —NH— or —NR ⁸ —, and R ⁹ and R ¹⁰ are bonded to each other and have 3 to 10 members including a nitrogen atom. It may form a ring heterocycle.
R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]

In formula (1a), -SO ₃ ^- if there is, the number is one.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ include phenyl, toluyl, xylyl, mesityl, propylphenyl and butylphenyl. And the like.

The aromatic hydrocarbon group substituent which may have a halogen _{^{atom, -R 8, -OH, -OR 8}} , -SO 3 -, -SO 3 H, -SO 3 - Z +, - _{^{CO 2 H, -CO 2 R 8}} , -SR 8, -SO 2 R 8, -SO 3 R 8 or _-SO 2 ^NR 9 ^{R 10} can be mentioned. Among them, as the _{^{substituent, -SO 3 -, -SO 3 H}} , -SO 3 - Z + and preferably _{^{-SO 2 NR 9 R 10, -SO}} 3 - Z + and _-SO 2 ^NR 9 ^{R 10} Is more preferred. -SO ₃ ^- as Z ^{+ _{is, -SO 3 - + N (R}} 11) 4 are preferred. When the colored curable resin composition of the present invention contains a compound of the formula (Ia) in which R ¹ , R ² , R ³ and R ⁴ are these groups, a color which is less likely to generate foreign matter and has excellent heat resistance. A filter can be formed from the colored curable resin composition.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms for R ¹ , R ² , R ³ , R ⁴ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ include a methyl group, an ethyl group, and a propyl group Butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, linear alkyl group such as icosyl group; isopropyl group, isobutyl group, isopentyl group, neopentyl group, A branched alkyl group such as a 2-ethylhexyl group; an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group; No.
The hydrogen atom contained in the saturated hydrocarbon group in R ¹ , R ² , R ³ and R ⁴ may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms, an acryloyl group, a methacryloyl group or a halogen atom. .
Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
The hydrogen atom contained in the saturated hydrocarbon group for R ⁸ may be substituted with a halogen atom.
The hydrogen atom contained in the saturated hydrocarbon group in R ⁹ and R ¹⁰ may be substituted with a hydroxy group or a halogen atom.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the ring containing a nitrogen atom formed by bonding R ¹ and R ² to each other and the ring containing a nitrogen atom formed by bonding R ³ and R ⁴ to each other include the following rings.

Examples of —OR ⁸ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, and an icosyloxy group.

Examples of —CO ₂ R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

Examples of -SR ⁸ include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.
Examples of —SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.
Examples of —SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

—SO ₂ NR ⁹ R ¹⁰ includes a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3 -Methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl , N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1 , 4-Dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group, N- (1,1,2 An N-1-substituted sulfamoyl group such as, 2,2-tetramethylbutyl) sulfamoyl group;
N, N-dimethylsulfamoyl, N, N-ethylmethylsulfamoyl, N, N-diethylsulfamoyl, N, N-propylmethylsulfamoyl, N, N-isopropylmethylsulfamo Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl And N, N-2-substituted sulfamoyl groups and the like.

R ^{5 _{is, -CO 2 H, -CO 2 -}} Z +, -CO 2 R 8, -SO 3 -, -SO 3 - Z +, -SO 3 H or _SO 2 NHR ⁹ are preferred, SO ₃ ^{-, _{-SO 3 - Z +, -SO 3}} H or _-SO 2 NHR ⁹ is more preferable.
m is preferably 1 to 4, more preferably 1 or 2.

Examples of the alkyl group having 1 to 6 carbon atoms in R ⁶ and R ⁷ include a linear alkyl group (methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group) and a branched alkyl group ( Isopropyl group, isobutyl group, etc.).

Examples of the aralkyl group having 7 to 10 carbon atoms in R ¹¹ include a benzyl group, a phenylethyl group, and a phenylbutyl group.

Z ⁺ is ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and is preferably ⁺ N (R ¹¹ ) ₄ .
^{As +} N (R ¹¹ ) ₄ , at least two of the four R ¹¹ are preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ¹¹ is preferably 20 to 80, and more preferably 20 to 60.
When the colored curable resin composition of the present invention has ⁺ N (R ¹¹ ) ₄ and R ¹¹ contains a compound represented by the formula (1a), which is one of these groups, the colored curable resin composition A color filter having less foreign matter than an object can be formed.
Examples of the halide ion represented by X ⁻ include a fluoride ion, a chloride ion, a bromide ion, and an iodide ion.

  The compound (1a) is preferably a compound represented by the formula (2a) (hereinafter, may be referred to as “compound (2a)”). Compound (2a) may be a tautomer thereof.

[In the formula (2a), R ²¹ , R ²² , R ²³ and R ²⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or It represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. R ²¹ and R ²² may combine with each other to form a ring containing a nitrogen atom, and R ²³ and R ²⁴ may combine with each other to form a ring containing a nitrogen atom.
R ²⁵ _is, ^-SO 3 _- represents a Z1 ⁺ or ^{_{-SO 2 NHR 26 -, -SO 3}} H, -SO 3.
m1 represents an integer of 0 to 5. When m1 is 2 or more, a plurality of R ²⁵ may be the same or different.
a1 represents an integer of 0 or 1.
X1 ^- represents a halide ion.
Z1 ^{+ _{is, + N (R 27) 4}} , Na + or an ^{K +,} 4 one ^{R 27} may be the same or different.
R ²⁷ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group. ]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms for R ²¹ , R ²² , R ²³ and R ²⁴ include those described as the aromatic hydrocarbon groups for R ¹ , R ² , R ³ and R ^4. And the same groups as mentioned above. Hydrogen atoms contained in the aromatic hydrocarbon _{^{group, -SO 3 -, -SO 3 H}} , -SO 3 - Z1 +, it may be substituted by -SO ^{3 R 26} or _-SO 2 ^{NHR 26.} R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and specific examples thereof include the same as the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ¹¹ .
As a combination of R ²¹ , R ²² , R ²³ and R ²⁴ , R ²¹ and R ²³ are a hydrogen atom, and R ²² and R ²⁴ are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. , hydrogen atoms contained in the aromatic hydrocarbon _{^{group, -SO 3 -, -SO 3 H}} , -SO 3 - Z1 +, is preferred combinations substituted with -SO ^{3 R 26} or _-SO 2 ^{NHR 26} . A more preferred combination is that R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and hydrogen contained in the aromatic hydrocarbon groups. atom, _-SO ³ - is a combination that has been substituted with Z1 ⁺ or _-SO 2 ^{NHR 26.} When R ^{21 to} R ²⁴ are these groups, a color filter having excellent heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (2a).

As a ring containing a nitrogen atom formed by R ²¹ and R ²² bonded to each other, and a ring containing a nitrogen atom formed by R ²³ and R ²⁴ bonded to each other, R ¹ and R ² are bonded to each other. The same ring as the ring containing a nitrogen atom to be formed can be mentioned. As the ring represented by R ²¹ and R ²² , an aliphatic heterocyclic ring is particularly preferred. Examples of the aliphatic heterocyclic ring include the following examples.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms for R ²⁶ and R ²⁷ include the same as the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms for R ¹¹ .
When R ²¹ , R ²² , R ²³ and R ²⁴ are monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms, they are preferably each independently a methyl group or an ethyl group.

The ^{R 26} in -SO ₃ R ²⁶ and _-SO 2 ^{NHR 26,} preferably branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 6 to 12 carbon atoms, 2- An ethylhexyl group is more preferred. When R ²⁶ is one of these groups, a color filter with less generation of foreign substances can be formed from the colored curable resin composition of the present invention containing the compound (2a).

Z1 ⁺ is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ .
^{As +} N (R ²⁷ ) ₄ , at least two of the four R ²⁷ are preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ²⁷ is preferably 20 to 80, and more preferably 20 to 60. When the colored curable resin composition of the present invention has a compound represented by the formula (2a) having ⁺ N (R ²⁷ ) ₄ and R ²⁷ is one of these groups, the colored curable resin composition A color filter with less generation of foreign substances can be formed.

  m1 is preferably 1 to 4, more preferably 1 or 2.

  The compound (1a) is also preferably a compound represented by the formula (3a) (hereinafter sometimes referred to as “compound (3a)”). Compound (3a) may be a tautomer thereof.

[In the formula (3a), R ³¹ and R ³² independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and are included in the saturated hydrocarbon group. _{more -CH} 2 - may, -O -, - CO- or ^{-NR 11} - it may be replaced by.
R ³³ and R ³⁴ independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.
R ³¹ and R ³³ may combine with each other to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may combine with each other to form a ring containing a nitrogen atom.
p and q each independently represent an integer of 0 to 5. When p is 2 or more, a plurality of R ³³ may be the same or different, and when q is 2 or more, a plurality of R ³⁴ may be the same or different.
R ¹¹ has the same meaning as described above. ]

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms for R ³¹ and R ³² include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. And a straight-chain alkyl group having 1 to 10 carbon atoms such as decyl group; a branched chain alkyl group having 3 to 10 carbon atoms such as isopropyl group, isobutyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; cyclopropyl And alicyclic saturated hydrocarbon groups having 3 to 10 carbon atoms, such as a group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
In R ³¹ and R ³² , the substituent which the saturated hydrocarbon group may have is an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with an alkoxy group having 1 to 3 carbon atoms. , A halogen atom, an acryloyl group and a methacryloyl group.
Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group.
Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.
Preferably, R ³¹ and R ³² are each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms (such as a methyl group, an ethyl group, or a propyl group).

The alkyl group having 1 to 4 carbon atoms for R ³³ and ^{R 34,} a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, sec- butyl group, and a tert- butyl group.
The alkylsulfanyl group having 1 to 4 carbon atoms for R ³³ and R ^34, methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, a butyl sulfanyl group and an isopropyl sulfanyl group.
The alkylsulfonyl group of 1 to 4 carbon atoms in R ³³ and R ^34, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, a butyl sulfonyl group and isopropylsulfonyl group.
R ³³ and R ³⁴ are preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

  p and q are each independently preferably an integer of 0 to 2, and preferably 0 or 1.

Examples of the xanthene compound include a compound represented by the formula (1-1) to a compound represented by the formula (1-48). In the formula, R ⁴⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group.

  As the xanthene compound, a compound represented by the formula (1-1) to a compound represented by the formula (1-8), a compound represented by the formula (1-11), and a compound represented by the formula (1-12) A compound represented by the formula (1-37): I. Acid Red 289, a sulfonamide, C.I. I. Acid red 289 quaternary ammonium salt, C.I. I. Acid violet 102 sulfonamide or C.I. I. A quaternary ammonium salt of Acid Violet 102 is preferred. In addition, the compounds represented by the formula (1-24) to the compounds represented by the formula (1-33) are also preferable in terms of excellent solubility in an organic solvent.

  As the xanthene dye (A1), a commercially available xanthene dye (for example, “Chugai Aminol Fast Pink RH / C” manufactured by Chugai Kasei Co., Ltd., “Rhodamin 6G” manufactured by Taoka Chemical Industry Co., Ltd.) is used. Can be. Further, it can be synthesized by using a commercially available xanthene dye as a starting material with reference to JP-A-2010-32999.

The cyanine dye (A2) is a dye containing, as a dye, only a cyanine compound, that is, a compound having in its molecule a structure in which an odd number of methine groups are conjugated and double-bonded between two heterocycles.
The content of the cyanine compound in the cyanine dye (A2) is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and particularly preferably 100% by mass.
As the cyanine compound, a compound represented by Formula (1b) or Formula (1c) is preferable.

[In formula (1b), ring Z ¹ and ring Z ² independently represent a heterocyclic ring which may be substituted.
Y ¹ , Y ² and Y ³ independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an aliphatic hydrocarbon group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms; Two selected from ¹ , Y ² and Y ³ may be bonded to each other to form a ring.
u represents an integer of 0 or more and 3 or less.
X ^b1- represents a counter anion, and b1 represents 1 or 2.

In formula (1c), ring Z ³ , ring Z ⁴ , ring Z ⁵ and ring Z ⁶ independently represent a heterocyclic ring which may be substituted.
Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ , Y ⁸ and Y ⁹ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an aliphatic hydrocarbon group having 1 to 8 carbon atoms or 6 carbon atoms. And 12 represents an aryl group, and two selected from Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ , Y ⁸ and Y ⁹ may be bonded to each other to form a ring.
L ¹ represents an optionally substituted divalent hydrocarbon group having 1 to 16 carbon atoms.
v and w each independently represent an integer of 0 or more and 3 or less.
X ^c1- represents a counter anion, and c1 represents 1 or 2.

The heterocyclic ring represented by ring Z ¹ , ring Z ² , ring Z ³ , ring Z ⁴ , ring Z ⁵ and ring Z ⁶ contains at least one heteroatom as a component of the ring, and may be a single ring. Or polycyclic.
The hetero atom may be any atom selected from elements of Group 15 or Group 16 in the periodic table, and examples thereof include a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom and a tellurium atom, and a nitrogen atom is preferable. , An oxygen atom and a sulfur atom, and more preferably a nitrogen atom.
Examples of the heterocycle include an indole ring, a benzoindole ring, an indolenine ring, a benzoindolenine ring, an oxazole ring, a benzoxazole ring, a thiazole ring, a benzothiazole ring, an imidazole ring, a benzimidazole ring, and a quinoline ring.

In the heterocyclic ring represented by ring Z ¹ , ring Z ² , ring Z ³ , ring Z ⁴ , ring Z ⁵ and ring Z ⁶ , the substituent is
C1-C6 fats such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and tert-pentyl group A group hydrocarbon group;
Aryl having 6 to 12 carbon atoms such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, and naphthyl group. Group;
An aralkyl group having 7 to 10 carbon atoms such as a benzyl group;
A C1-C6 alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group and a pentyloxy group;
An aryloxy group having 6 to 10 carbon atoms such as a phenoxy group;
An aralkyloxy group having 7 to 10 carbon atoms such as a benzyloxy group;
A group having an ester bond such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an acetoxy group, a benzoyloxy group;
Methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl, n-propylsulfamoyl, di-n-propylsulfamoyl, isopropylsulfamoyl, diisopropylsulfamoyl An alkylsulfamoyl group having 1 to 8 carbon atoms such as a famoyl group, an n-butylsulfamoyl group, a di-n-butylsulfamoyl group, a 2-ethylhexylsulfamoyl group;
Alkylsulfonyl groups having 1 to 6 carbon atoms such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, isobutylsulfonyl group, sec-butylsulfonyl group and tert-butylsulfonyl group;
Halogen atoms such as fluorine, chlorine, bromine and iodine;
Vinyl, allyl, propen-2-yl, methallyl, but-3-en-1-yl, but-3-en-2-yl, but-3-en-3-yl, penta An alkenyl group having 2 to 6 carbon atoms such as -4-en-1-yl group;
A nitro group; a cyano group;
When such a substituent has a hydrogen atom, examples of the hydrogen atom include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. An alkoxy group such as isobutoxy group, sec-butoxy group, tert-butoxy group and pentyloxy group; an aryloxy group such as phenoxy group and benzyloxy group; a carboxy group; a cyano group; a nitro group; an acryloyloxy group; It may be substituted by a group or the like.

Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by any of Y ^{1 to} Y ⁹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group and a tert. -A butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group and a cyclohexyl group.
Examples of the aryl group having 6 to 12 carbon atoms represented by any of Y ^{1 to} Y ⁹ include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a xylyl group, a mesityl group, and an o-cumenyl group. Group, m-cumenyl group, p-cumenyl group, naphthyl group and the like.

The heterocycle represented by any one of ring Z ¹ , ring Z ² , ring Z ³ , ring Z ⁴ , ring Z ⁵ and ring Z ⁶ includes an indole ring, a benzoindole ring, an indolenine ring and a benzoindolenine ring Are preferable, and an indole ring and an indolenine ring are more preferable.
The heterocycle represented by any of ring Z ¹ , ring Z ² , ring Z ³ , ring Z ⁴ , ring Z ⁵ and ring Z ⁶ has one or two alkyl groups or halogen atoms as substituents. Is preferred.
Y ^{1 to} Y ⁹ represent a hydrogen atom, a cyano group, a halogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms, or two of Y ^{1 to} Y ³ or two of Y ^{4 to} Y ⁹ It is preferable that they form a ring together, more preferably a hydrogen atom, a cyano group or a halogen atom, and even more preferably a hydrogen atom.
u, v and w are preferably 1 from the viewpoint of the brightness of the obtained color filter.

Examples of the divalent hydrocarbon group representing L ¹ include alkanediyl groups such as a methylene group, an ethylene group, an ethanediyl group, a propanediyl group, a butanediyl group, a tetramethylene group, a pentamethylene group, and a hexamethylene group;
Divalent alicyclic hydrocarbon groups such as cyclopentanediyl group, cyclohexanediyl group and cyclohexenediyl group;
divalent aromatic hydrocarbon groups such as o-phenylene group, m-phenylene group, p-phenylene group and naphthylene group; and the like.
Examples of the substituent which the divalent hydrocarbon group may have include an amino group, a carboxy group, a cyano group, a nitro group, a halogen atom, a hydroxy group and the like.
L ¹ may be bonded to any position of the ring Z ¹ and the ring Z ³ .
The divalent hydrocarbon group is preferably an alkanediyl group having 1 to 16 carbon atoms, more preferably an alkanediyl group having 1 to 10 carbon atoms, and still more preferably an alkanediyl group having 3 to 8 carbon atoms.

^Examples of the counter anion representing X ^b1− or X ^c1− include a halide ion, ClO ₄ ⁻ , OH ⁻ , an organic carboxylate anion, an organic sulfonate anion, a Lewis acid anion, an organic metal complex anion, a dye-derived anion, and an organic sulfonyl. Examples include an imidate anion and an organic sulfonylmethide anion.
Examples of the halide ion include Cl ⁻ , Br ⁻ , and I ⁻ .
Examples of the organic carboxylate anion include benzoate ion, alkanoate ion, trihaloalkanoate ion, nicotinate ion and the like.
Examples of the organic sulfonic acid anion include a benzenesulfonic acid ion, a naphthalenesulfonic acid ion, a p-toluenesulfonic acid ion, and an alkanesulfonic acid ion.
Examples of Lewis acid anions include BF ₄ ⁻ , SbF ₆ ^{− and the} like.
Examples of the dye-derived anion include an anion derived from a phthalocyanine compound, an anion derived from an azo compound, and the like, and preferably an anion derived from a phthalocyanine compound.

The organometallic complex anion is composed of a central metal and a ligand. Examples of the ligand include an azo ligand, a bisphenyldithiol ligand, a thiocatechol chelate ligand, and a thiobisphenolate chelate. And a ligand such as a bisdiol-α-diketone-based ligand. As the central metal, transition metals of Groups 3 to 11 in the periodic table, for example, scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, Examples include iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, cadmium, and mercury.
As the above-mentioned ligand, an azo-based ligand or a bisphenyldithiol-based ligand is preferred, and an azo-based ligand is more preferred.
Examples of the organic sulfonyl imidate anion include a bis (trifluoromethanesulfonyl) imidate anion, a bis (nonafluorobutanesulfonyl) imidate anion, and a trifluoromethanesulfonylpentafluorophenylsulfonylimidate anion.
Examples of the organic sulfonylmethide anion include a tris (trifluoromethanesulfonyl) imidate anion, a tris (nonafluorobutanesulfonyl) imidate anion, and the like.
As the above-mentioned central metal, cobalt, nickel and copper are preferable in view of production cost and ease of handling.
Specifically, the organometallic complex anion is preferably an azo metal complex anion whose central metal is cobalt, nickel or copper or a bisphenyldithiol metal complex anion, and is preferably an azo metal complex anion whose central metal is cobalt, nickel or copper. Metal complex anions are more preferred.

  As the compound represented by the formula (1b), a compound represented by the formula (2b) is preferable.

[In formula (2b), ring Z ⁷ and ring Z ⁸ each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent.
Y ^{1 to} Y ³ , u, X ^b1− and b1 have the same ^{meanings as} in the formula (1b).
Y ¹⁰ and Y ¹¹ independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
Y ¹² and Y ¹³ each independently represent a hydrogen atom, a halogen atom, or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, or ¹² and one Y ¹³ are bonded to each other to represent a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms.
p1 and p2 independently represent an integer of 0 or more and 2 or less. ]

Examples of the monovalent aliphatic hydrocarbon group for Y ¹⁰ , Y ¹¹ , Y ¹² and Y ¹³ include a methyl group, an ethyl group, a vinyl group, an ethynyl group, a propyl group, an isopropyl group, an isopropenyl group, an allyl group and a propene group. 2-yl group, propynyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, but-3-en-2-yl group, buta-1,3-dien-2-yl group, pentyl group , Isopentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group, penta-2-en-4-yl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group, Examples thereof include a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms such as an octyl group.

Examples of the substituent in the monovalent aliphatic hydrocarbon group include, for example,
C6-C12 aromatic hydrocarbons such as phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, mesityl, o-cumenyl, m-cumenyl, p-cumenyl and the like. Group;
C1-C8 alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, phenoxy group and benzyloxy group;
Halogen atoms such as fluorine, chlorine, bromine and iodine;
A hydroxy group; a carboxy group; a nitro group; a cyano group.

Examples of the divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms in which one Y ¹² and one Y ¹³ are bonded to each other include a methylene group, an ethylene group, a propanediyl group, and a butanediyl group.

Y ¹⁰ and Y ¹¹ are each independently preferably an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, and an alkyl group having 1 to 5 carbon atoms which may be substituted with a halogen atom. More preferably, it is a group.
Y ¹² and Y ¹³ are each independently preferably an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom, and more preferably a methyl group or a trifluoromethyl group. Y ¹² and Y ¹³ are preferably the same group.

  Examples of the cyanine compound include compounds represented by any of formulas (2b-1) to (2b-19) and compounds described in JP-A-2015-118267.

The anion derived from the xanthene compound in the salt of the anion derived from the xanthene compound and the cation derived from the cyanine compound includes an anion derived from the compound (1a).
Examples of the cation derived from the cyanine compound include a cation in the compound represented by the formula (1b) or the formula (2b).
Examples of the salt of the anion derived from the xanthene compound and the cation derived from the cyanine compound include salts represented by the following formula. The salt of the anion and the cation can be synthesized according to the method described in WO 2013/050341.

<Blue pigment>
As the blue pigment, for example, a blue pigment classified as a pigment in a color index (published by The Society of Dyers and Colorists), specifically, C.I. I. And blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60. I. Pigment Blue 15: 3 and C.I. I. Pigment Blue 15: 6 is preferred, and C.I. I. Pigment Blue 15: 6 is more preferred.

<Blue or purple dye (dye (A4))>
The blue or purple dye means a dye having a maximum absorption wavelength in a range of 560 nm to 650 nm in a chloroform solution. The blue or violet dye is preferably a dye having a maximum absorption wavelength in the range of 580 nm to 650 nm, and more preferably a dye having a maximum absorption wavelength in the range of 600 nm to 645 nm.
In addition, the dye (A4) is a dye different from the dyes of the xanthene dye (A1) and the cyanine dye (A2), and is also a dye different from the salt of the anion derived from the xanthene compound and the cation derived from the cyanine compound. .
The dye (A4) includes a triarylmethane dye, a tetraazaporphyrin dye, an anthraquinone dye, and a dye containing only the compound represented by the formula (A7) as a dye (hereinafter, a compound represented by the dye (A7) is referred to as a “dye ( A7)), and is preferably at least one selected from the group consisting of
More preferably, it is at least one selected from the group consisting of a triarylmethane dye and a dye (A7).

A triarylmethane dye is a dye containing only a compound having a structure in which three aromatic hydrocarbon groups are bonded to one carbon atom (hereinafter, may be referred to as a triarylmethane compound) as a dye.
As the triarylmethane dye, for example,
C. I. Acid Violet (hereinafter, description of CI Acid Violet is omitted and only the number is described) 15, 16, 17, 19, 21, 23, 24, 25, 38, 49, 72,
C. I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 22, 24, 26, 34, 38, 48, 75, 83, 84, 86, 88, 90, 90: 1, 91, 93, 93: 1, 99, 100, 103, 104, 108, 109, 110, 119, 123, 147, 213, 269,
C. I. Basic Blue 7, 81, 83, 88, 89,
C. I. Basic Violet 2,
C. I. Direct Blue 1, 3, 28, 29, 41, 42, 47, 52, 55,
C. I. Food violet 3,
C. I. Modant violet 1, 1: 1, 3, 6, 8, 10, 11, 15, 16, 17, 18, 19, 21, 23, 27, 28, 33, 36, 39, 49,
And the like.

  The triarylmethane dyes also include the compounds described below.

The tetraazaporphyrin dye is a dye containing only a compound having a tetraazaporphyrin skeleton in a molecule as a dye.
Examples of the tetraazaporphyrin dye include the compounds described below.

An anthraquinone dye is a dye containing only a compound having an anthraquinone skeleton in a molecule as a dye.
As anthraquinone dyes, for example,
C. I. Solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60,
C. I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139,
C. I. Acid Violet 34,
C. I. Acid Blue 25, 27, 40, 45, 78, 80, 112
C. I. Disperse Violet 26, 27,
C. I. Disperse Blue 1, 14, 56, 60,
C. I. Direct Blue 40,
C. I. Modant Blue 8
And the like.

  Examples of the anthraquinone dye include the compounds described below.

  Examples of the dye (A7) include a compound represented by the formula (A7) and a tautomer thereof.

[In the formula (A7),
g represents an arbitrary natural number.
G ^g- represents a g-valent anion.
D represents an aromatic heterocyclic group which may have a substituent.
R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group or a saturated hydrocarbon group; -CH ₂ contained in the hydrocarbon group - may be replaced by -O-.
R ^21A and R ^22A independently represent an ^optionally substituted amino group. ]

Examples of the saturated hydrocarbon group represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n- C1-C20 alkyl such as butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, etc. Groups: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, decahydronaphthyl, adamantyl, 2-alkyladamantane 2-yl group, 1- (adamantan-1-yl) alkane-1- Group, norbornyl group, alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as methyl norbornyl group and an isobornyl group. Preferably it is a C1-C8 alkyl group, More preferably, it is a C1-C6 alkyl group, More preferably, it is a C1-C4 alkyl group.
^{R 1A, R 2A, R 3A} , R 4A, R 5A, R 6A, -CH 2 contained in the saturated hydrocarbon groups represented by ^{R 7A} and ^{R 8A} - may be replaced by -O-.
Specific examples of the group in which —CH ₂ — contained in the saturated hydrocarbon group is replaced by —O— include the following groups (* represents a bond), and preferably has 1 to 1 carbon atoms. -CH ₂ contained in the alkyl group having 10 - can be mentioned a group are replaced by -O-, more preferably -CH ₂ contained in the alkyl group having 1 to 6 carbon atoms - are replaced by the -O- Groups.

Examples of the halogen atom represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and preferably fluorine. Atom or chlorine atom.

R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A are each independently preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably a hydrogen atom or methyl. And more preferably a hydrogen atom.

The hydrogen atom contained in the amino group represented by R ^21A and R ^22A is an aryl group which may have a substituent, an alkyl group which may have a substituent, or an acryloyl group or a methacryloyl group. May be substituted by a group containing

  In the aryl group which may have a substituent, examples of the aryl group include an aryl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and an anthryl group. Examples of the substituent which may be present include a halogen atom.

In the alkyl group which may have a substituent, the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, Examples thereof include an alkyl group having 1 to 20 carbon atoms such as a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group and a group. Other -CH 2 _{- -} -CH 2 in the coupling position of the nitrogen atom contained in the alkyl group may be replaced by -O-, Examples of the substituent that the said alkyl group optionally having , An amino group, a substituted amino group, a group containing a halogen atom and a silicon atom.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the substituted amino group include a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a butylamino group, a sec-butylamino group, a tert-butylamino group, a dimethylamino group, a diethylamino group, a dipropylamino group, Examples thereof include an alkylamino group having 1 to 8 carbon atoms such as an ethylmethylamino group and a dialkylamino group having 1 to 8 carbon atoms.
Examples of the group containing a silicon atom include a trialkoxysilyl group such as a trimethoxysilyl group and a triethoxysilyl group; and an alkyldialkoxysilyl group such as a methyldimethoxysilyl group and a methyldiethoxysilyl group.

The group containing an acryloyl group or a methacryloyl group means a group having at least one acryloyl group or methacryloyl group.
The carbon number of the group containing the acryloyl group or the methacryloyl group is usually 3 to 30, preferably 3 to 20.
The group containing an acryloyl group or a methacryloyl group is preferably a group containing an acryloyloxy group or a methacryloyloxy group.
The group containing an acryloyl group or a methacryloyl group is preferably a group represented by the formula (A7-1).

[In the formula (A7-1), R ^15A represents an acryloyl group or a methacryloyl group.
R ^14A represents an alkanediyl group having 1 to 8 carbon atoms, and —CH ₂ — contained in the alkanediyl group may be replaced by —O—.
* Represents a bond to a nitrogen atom. ]

Examples of the alkanediyl group having 1 to 8 carbon atoms represented by R ^14A include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group. Hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-1, 2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1 , 4-diyl group and 2-methylbutane-1,4-diyl group, preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably a methylene group or an ethylene group, further preferably a methylene group. It is.

  Examples of the group containing an acryloyl group or a methacryloyl group include the following groups. (* Represents a bond to the nitrogen atom.)

^Examples of the ^optionally substituted amino group represented by R ^21A and R ^22A include a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a butylamino group, an isobutylamino group, a sec-butylamino group, tert-butylamino group, pentylamino group, neopentylamino group, hexylamino group, dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, ethylmethylamino group, ethylisopropylamino group, ethylpropylamino group, Isopropylmethylamino group, isopropylpropylamino group, methylpropylamino group, phenylamino group, naphthylamino group, 2-methylphenylamino group, 4-methylphenylamino group, 3-methylphenylamino group, 3,5-dimethylphenyl Mino group, 4-ethylphenylamino group, N-methyl-N-phenylamino group, acryloyloxymethylamino group, N- (acryloyloxymethyl) -N-methylamino group, N- (acryloyloxyethyl) -N- An ethylamino group, an N- (methacryloyloxyethyl) -N-ethylamino group, an N- (acryloyloxyethyl) -N-phenylamino group, an N- (acryloyloxyethyl) -N- (methacryloyloxymethyl) amino group, N- (acryloyloxyethyloxymethyl) -N-ethylamino group and N- (methacryloyloxyethyloxymethyl) -N-ethylamino group are exemplified.

The aromatic heterocyclic group only needs to have at least one hetero atom, and examples of the hetero atom include a nitrogen atom, an oxygen atom and a sulfur atom.
The aromatic heterocyclic group represented by D may be monocyclic or polycyclic.
Examples of the aromatic heterocyclic group represented by D include pyridyl group, imidazolyl group, pyrazolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, benzothiazolyl group, benzoisothiazolyl group, thienyl group, benzothienyl group and the like. And an aromatic heterocyclic group having 2 to 8 carbon atoms containing at least one nitrogen atom or sulfur atom as a component of the ring is preferable.
Examples of the substituent which the aromatic heterocyclic group represented by D may have include an amino group which may be substituted, an alkyl group having 1 to 20 carbon atoms, and an aryl which may have a substituent And preferably an amino group which may be substituted and an aryl group which may have a substituent.

^Examples of the optionally substituted amino group include the same as the ^optionally substituted amino group represented by R ^21A and R ^22A .
Examples of the alkyl group having 1 to 20 carbon atoms include the same groups as the alkyl groups having 1 to 20 carbon atoms represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A. No.
Examples of the aryl group which may have a substituent include a phenyl group, a tolyl group, a xylyl group, a naphthyl group and an anthryl group, and the substituent includes a fluorine atom, a halogen atom such as a chlorine atom and a bromine atom. No.

  The aromatic heterocyclic group represented by D is preferably a group represented by the formula (III).

[In the formula (III), X represents an oxygen atom or a sulfur atom.
R ⁵⁵ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group which may have a substituent.
R ⁵⁶ represents an amino group which may be substituted.
* Represents a bond to a carbon atom. ]

Examples of the alkyl group having 1 to 20 carbon atoms represented by ^{R 55, R 1A, R 2A} , R 3A, R 4A, R 5A, R 6A, C 1 -C 20 atoms represented by ^{R 7A} and ^{R 8A} The same as the alkyl group can be mentioned.
^Examples of the aryl group which may have a substituent represented by R ⁵⁵ include a phenyl group.
^Examples of the optionally substituted amino group represented by R ⁵⁶ include the same as the ^optionally substituted amino group represented by R ^21A and R ^22A .

R ⁵⁵ is preferably an unsubstituted or substituted aryl group, and more preferably an unsubstituted or substituted aryl group.
R ⁵⁶ is preferably an amino group which may be substituted, and more preferably a substituted amino group represented by —N (R ^56a ) (R ^56b ).

[R ^56a represents an alkyl group having 1 to 8 carbon atoms, and R ^56b represents a phenyl group which may have an alkyl group having 1 to 4 carbon atoms. ]

  Examples of the aromatic heterocyclic group represented by D include groups represented by the formula (III-1) to groups represented by the formula (III-8), and are preferably represented by the formula (III-1) or the formula (III-1). It is a group represented by (III-2).

In the formula (A7), g is an arbitrary natural number, preferably 1 or 2, and more preferably 1.
G ^g- represents a g-valent anion, and is not limited as long as it forms a salt with the cation and the g-valent anion. For example, when g is a natural number of 2 or more, it may have one g-valent anion or g monovalent anions.
G ^g- preferably has g monovalent anions, and is represented by, for example, a halide ion such as a fluoride ion, a chloride ion, a bromide ion and an iodide ion, or a formula (y1). Anion represented by the formula (y2) and an anion represented by the formula (y3).

[In the formula (y1), R ^B1 represents a hydrocarbon group which may have a halogen atom.
In the formula ^{(y2), R B2} and ^{R B3} are, independently of each other, represent a halogen atom or a halogenated hydrocarbon group, or ^{R B2} and ^{R B3} are bonded to _-SO 2 ^-N together - -SO ₂ Forming a ring containing-.
In the formula (y3), M represents an aluminum atom or a boron atom, and R ^B4 and R ^B5 each independently represent a phenylene group which may have a substituent. ]

The hydrocarbon group represented by R ^B1, include saturated hydrocarbon group and aromatic hydrocarbon group having 6 to 14 carbon atoms having 1 to 8 carbon atoms.
Examples of the saturated hydrocarbon group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, and a heptyl group. And alkyl groups such as 2-ethylhexyl group and octyl group; and alicyclic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and methylcyclohexyl group.
Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
Examples of the halogenated alkyl group having 1 to 8 carbon atoms include difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, and perfluoro. Ethyl group, 1,1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) -1,2,2 2,2-tetrafluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group, 1,1,2,2 , 3,3,4,4-octafluorobutyl group, perfluorobutyl group, dibromomethyl group and tribromomethyl group, and preferably a fluoroalkyl group having 1 to 8 carbon atoms. That.
Examples of the aromatic hydrocarbon group having a halogen atom having 6 to 14 carbon atoms include a phenyl group having a halogen atom and a naphthyl group having a halogen atom. Specific examples include a fluorophenyl group, a chlorophenyl group, a bromophenyl group, a difluorophenyl group, a 1-fluoro-4-chlorophenyl group, a trifluorophenyl group, and a fluoronaphthyl group.

^RB1 is preferably a halogenated alkyl group having 1 to 8 carbon atoms, and more preferably a fluorinated alkyl group having 1 to 8 carbon atoms.

The halogen atom represented by ^RB2 and ^RB3 includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and is preferably a fluorine atom or a chlorine atom.
Examples of the halogenated hydrocarbon group represented by R ^B2 and R ^B3, and an aromatic hydrocarbon group having 6 to 14 carbon atoms having a halogenated alkyl group having 1 to 8 carbon atoms, a halogen atom.
Examples of the halogenated alkyl group having 1 to 8 carbon atoms include difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, and perfluoro. Ethyl group, 1,1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) -1,2,2 2,2-tetrafluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group, 1,1,2,2 , 3,3,4,4-octafluorobutyl group, perfluorobutyl group, dibromomethyl group and tribromomethyl group, and preferably a fluoroalkyl group having 1 to 8 carbon atoms. That.
Examples of the aromatic hydrocarbon group having a halogen atom having 6 to 14 carbon atoms include a phenyl group having a halogen atom and a naphthyl group having a halogen atom. Specific examples include a fluorophenyl group, a chlorophenyl group, a bromophenyl group, a difluorophenyl group, a 1-fluoro-4-chlorophenyl group, a trifluorophenyl group, and a fluoronaphthyl group.

Preferably, R ^B2 and R ^B3 are the same group.
Preferably, ^RB2 and ^RB3 are each independently a fluoroalkyl group having 1 to 8 carbon atoms, more preferably a trifluoromethyl group.

As the substituent which the phenylene group represented by ^RB4 and ^RB5 may have, a hydroxy group is preferable.
R ^B4 and R ^B5 are preferably the same group.

  Examples of the anion represented by the formula (y1) include a methanesulfonic acid anion, a toluenesulfonic acid anion, a dodecylbenzenesulfonic acid anion, a trifluoromethanesulfonic acid anion, a perfluorobutanesulfonic acid anion, a phenylsulfonic acid anion, and a fluorophenylsulfonic acid anion. And the like.

  Examples of the anion represented by the formula (y2) include the following anions.

  Examples of the anion represented by the formula (y3) include the anions described below.

  Examples of the compound represented by the formula (A7) include compounds represented by the formulas (AI-a1) to (AI-a17), and preferably represented by the formula (AI-a5). And a compound represented by the formula (AIla17) and a compound represented by the formula (AIla17).

  The compound represented by the formula (A7) can be produced, for example, by the method described in Japanese Patent Application Publication No. 2015-28121.

The dye (A4), the xanthene dye (A1) and the cyanine dye (A2) may be a monomer or a polymer.
When the xanthene dye (A1) is a polymer, the xanthene dye (A1) may be a structural unit derived from a xanthene compound having a polymerizable group such as one or more ethylenically unsaturated bonds (hereinafter sometimes referred to as a “xanthene unit”). ), And may be a polymer comprising only xanthene units, or a copolymer containing xanthene units and other structural units (hereinafter, may be referred to as a copolymer (a1)). There may be.
Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an isocyanate group, and the like.
Examples of other structural units in the copolymer (a1) include structural units derived from a monomer having an ethylenically unsaturated bond, and the structural units include the following formulas (1) to (3) And a structural unit constituting the resin (B) described later.

When the cyanine dye (A2) is a polymer, it is a polymer containing a structural unit derived from a cyanine compound having one or more polymerizable groups (hereinafter sometimes referred to as “cyanine unit”), and a polymer consisting of only a cyanine unit. Or a copolymer containing a cyanine unit and another structural unit (hereinafter sometimes referred to as a copolymer (a2)).
Other structural units in the copolymer (a2) include, for example, structural units derived from a monomer having an ethylenically unsaturated bond, and the structural units include the following formulas (1) to (3) And a structural unit constituting the resin (B) described later.

When the dye (A4) is a polymer, a structural unit derived from a compound having at least one polymerizable group among the compounds listed as the dye (A4) (hereinafter, may be referred to as “(A4) unit”) ), And may be a polymer consisting of only the (A4) unit, or a copolymer containing the (A4) unit and another structural unit (hereinafter, referred to as a copolymer (a3)). ).
Other structural units in the copolymer (a3) include, for example, structural units derived from a monomer having an ethylenically unsaturated bond, and the structural units include the following formulas (1) to (1). The structural unit represented by (3) and the structural unit constituting the resin (B) described later are exemplified.
The copolymer (a1) and the copolymer (a2) may contain (A4) units.

[In the formula (1), R ¹¹⁹ and R ¹¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, or a carbon number which may have a substituent. Represents an aryl group having 6 to 30 or an aralkyl group having 7 to 30 carbon atoms which may have a substituent;
m ′ represents an integer of 0 to 5. ]

[In the formula (2), R ¹¹¹ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent or Represents an aralkyl group having 7 to 30 carbon atoms which may have a substituent.
R ¹¹² represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, —CO—R ¹¹⁷ —COOH, or a compound thereof. Indicates a combination.
R ¹¹⁷ represents an alkylene group having 1 to 30 carbon atoms which may have a substituent or an oxyalkylene group having 1 to 30 carbon atoms which may have a substituent. ]

[In the formula (3), R ¹¹³ and R ¹¹⁴ independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, or a carbon number which may have a substituent. Represents an aryl group having 6 to 30 or an aralkyl group having 7 to 30 carbon atoms which may have a substituent;
R ¹¹⁵ represents -COOH or -CONHR ¹¹⁸ .
R ¹¹⁸ represents an alkyl group having 1 to 30 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent.
R ¹¹⁶ represents -COOH, or R ¹¹⁵ and R ^{116 taken} together represent -CO-O-CO- or -CO-NR ¹¹⁸ -CO-. ]

In addition, as a structural unit derived from a monomer having an ethylenically unsaturated bond and other than a structural unit that is any of a xanthene unit, a cyanine unit and a (A4) unit, a resin (B )), A structural unit derived from (b) or (c), and preferably an alkenyl aromatic monomer such as styrene, α-methylstyrene, vinyltoluene and methoxystyrene;
Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate Unsaturated carboxylic acid ester compounds such as cyclohexyl methacrylate, phenyl acrylate and phenyl methacrylate;
Unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, and 2-dimethylaminoethyl methacrylate;
Vinyl carboxylate compounds such as vinyl acetate and vinyl benzoate;
Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl acrylate and glycidyl methacrylate;
Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile;
Unsaturated amide compounds such as acrylamide and methacrylamide;
Dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide and N-benzylmaleimide;
And a structural unit derived from

It is preferable that the copolymer (a1), the copolymer (a2) and the copolymer (a3) include a structural unit having a carboxy group as another structural unit. The monomer that leads to the structural unit having a carboxy group is a monomer having an ethylenically unsaturated bond and one or more carboxy groups. Specifically, (a) in the resin (B) described below is And acrylic acid, methacrylic acid, maleic acid, itaconic acid and fumaric acid.
The mass ratio of the monomer which leads to the structural unit having a carboxy group is usually from 1 to 50% by mass, preferably from 3 to 40% by mass, based on the total mass of the monomers used for producing the copolymer. And more preferably 5 to 30% by mass.

As the xanthene unit, each structural unit derived from the compound represented by the formula (1-45) to the compound represented by the formula (1-47) is preferable.
As the cyanine unit, each structural unit derived from the compound represented by the formula (2b-14) to the compound represented by the formula (2b-15) is preferable.
The (A4) unit contained in the copolymer (a3) is at least one selected from the group consisting of a structural unit derived from a triarylmethane compound and a structural unit derived from the compound represented by the formula (A7). Is preferred.
As the structural unit derived from the triarylmethane compound, the compound represented by the formula (2b-1) to the compound represented by the formula (2b-4) and the compound represented by the formula (2b-6) to the formula Each structural unit derived from the compound represented by (2b-13) is preferable.
As the structural unit derived from the compound represented by the formula (A7), a structural unit derived from the compound represented by the above formula (AI-a15) is preferable.

Examples of other pigments (A3) include pigments other than blue pigments among pigments classified as pigments in the Color Index (published by The Society of Dyers and Colorists).
Specifically, 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, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as Pigment Green 7, 36, 58;
C. I. Brown pigments such as Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.

  Other pigments include C.I. I. Violet color pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 are preferred. I. Pigment Violet 23 is more preferred.

  The pigment preferably has a uniform particle size. By performing a dispersion treatment by adding a pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more. Examples of the pigment dispersants include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Corporation), EFKA (manufactured by CIBA), Ajispar (manufactured by CIBA) Techno Co., Ltd.) and Disperbyk (by Big Chemie).
When a pigment dispersant is used, its amount is preferably from 1% by mass to 100% by mass, more preferably from 5% by mass to 50% by mass, based on the total amount of the pigment. When the amount of the pigment dispersant used is in the above range, a pigment dispersion having a uniform dispersion state tends to be obtained.

The content of the xanthene dye (A1) is preferably from 1 to 97% by mass, more preferably from 1 to 50% by mass, and still more preferably from 1 to 30% by mass, based on the total amount of the colorant (A). And particularly preferably 2 to 15% by mass.
The content of the cyanine dye (A2) is preferably from 1 to 97% by mass, more preferably from 1 to 50% by mass, and still more preferably from 1 to 30% by mass, based on the total amount of the colorant (A). And particularly preferably 1 to 10% by mass.
The content ratio of the xanthene dye (A1) to the cyanine dye (A2) (= xanthene dye (A1): cyanine dye (A2), mass ratio) is preferably from 10:90 to 90:10, and 25: The ratio is more preferably from 75 to 75:25.
When the colored curable resin composition of the present invention contains a salt of an anion derived from a xanthene compound and a cation derived from a cyanine compound, the content of the salt is preferably based on the total amount of the colorant (A). It is 1 to 97% by mass, more preferably 1 to 50% by mass, further preferably 1 to 30% by mass, particularly preferably 2 to 20% by mass.
The content of the blue pigment is preferably from 1 to 98% by mass, more preferably from 20 to 98% by mass, and still more preferably from 40 to 98% by mass, based on the total amount of the colorant (A).
When the coloring curable resin composition of the present invention contains the dye (A4), its content is preferably from 1 to 90% by mass, more preferably from 5 to 90% by mass, based on the total amount of the coloring agent (A). It is 75% by mass, more preferably 10 to 60% by mass.
When the other pigment (A3) is contained in the colored curable resin composition of the present invention, its content is preferably 0.1 to 30% by mass based on the total amount of the colorant (A). Preferably it is 0.1-20 mass%, More preferably, it is 0.1-10 mass%.

  In the colored curable resin composition of the present invention, the content of the coloring agent (A) is preferably from 5 to 60% by mass, more preferably from 8 to 55% by mass, based on the total amount of solids, More preferably, it is 10 to 50% by mass. When the content of the colorant (A) is within the above range, the color density of the color filter is sufficient, and the resin (B) and the polymerizable compound (C) are contained in a required amount in the composition. Therefore, a pattern having sufficient mechanical strength can be formed. Here, the “total amount of solid content” in the present specification refers to an amount obtained by removing the content of the solvent from the total amount of the colored curable resin composition. The total amount of the solid content and the content of each component with respect to the solid content can be measured by a known analytical means such as liquid chromatography or gas chromatography.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].
Resin [K1]; at least one kind (a) (hereinafter sometimes referred to as “(a)”) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and a cyclic ether having 2 to 4 carbon atoms A copolymer of 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) (however, (a) and (b) are different) (hereinafter “(c)”) A copolymer);
Resin [K3]; a copolymer of (a) and (c);
Resin [K4]; a resin obtained by reacting (b) with a copolymer of (a) and (c);
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 with a carboxylic anhydride.

As (a), specifically, for example, 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-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic 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] bicyclo unsaturated compounds containing a carboxy group such as hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of di- or higher-valent polycarboxylic acids such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] phthalate ;
Examples include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferred from the viewpoint of copolymerization reactivity and the solubility of the obtained resin in an aqueous alkali solution.

As (b), for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond Is mentioned. (B) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.
In the present specification, “(meth) acrylic acid” refers to 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)”) and a monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”) and the like. No.

  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) includes glycidyl (meth) acrylate, β-methyl glycidyl (meth) acrylate, β-ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (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 can be mentioned.

  Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Corporation), and 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), compound represented by formula (I) and formula (II) And the like.

[In the formulas (I) and (II), R ^a and R ^b 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. You may.
X ^a and ^{X b} is a single ^{bond, -R c -, * - R} c -O -, * - represents the R c -S- or ^* -R c -NH-.
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and a 1-hydroxy Examples thereof include a -1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
^Ra and ^Rb preferably include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane- 1,6-diyl group and the like.
The X ^a and ^{X b,} preferably a single bond, a methylene group, an ethylene group, * _- CH 2 -O- and _* -CH ₂ CH ₂ -O- and the like, more preferably a single bond, * - CH ₂ CH ₂ —O— (* represents a bond to O).

  Examples of the compound represented by the formula (I) include compounds represented by any of the formulas (I-1) to (I-15). Among them, Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9) or Formulas (I-11) to (I-15) The compound represented by Formula (I-1), Formula (I-7), Formula (I-9) or Formula (I-15) is more preferred.

  Examples of the compound represented by the formula (II) include compounds represented by any of the formulas (II-1) to (II-15). Among them, Formula (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula (II-9) or Formula (II-11) to Formula (II-15) The compound represented by Formula (II-1), Formula (II-7), Formula (II-9) or Formula (II-15) is more preferred.

  The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of two or more. When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, their content ratio [the compound represented by the formula (I): the compound represented by the formula (II)] On a molar basis, it is preferably from 5:95 to 95: 5, more preferably from 20:80 to 80:20.

  As (b2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. (B2) includes 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane And 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, and 3-ethyl-3-acryloyloxyethyl oxetane.

  As (b3), a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

  (B) is preferably (b1) in that the reliability of the obtained color filter, such as heat resistance and chemical resistance, can be further improved. Furthermore, (b1-2) is more preferable in that the storage stability of the colored curable resin composition is excellent.

As (c), 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 ] decane-8-yl (meth) acrylate (in the art, this is commonly used as "dicyclopentanyl (meth) acrylate". In the case of "tricyclodecyl (meth) acrylate" There is.), Bird Black (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) [5.2.1.0 ^2,6] decene-8-yl (meth) acrylate, dicyclopenta Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylates;
Hydroxy group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (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 (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclo unsaturated 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, methoxystyrene, (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Among them, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferred from the viewpoint of copolymerization reactivity and heat resistance. preferable.

In the resin [K1], the ratio of the structural units derived from each of the resins [K1] is defined as:
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 unit of the resin [K1] is in the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the obtained color filter are excellent. Tend.

  The resin [K1] can be obtained, for example, by the method described in the document "Experimental Method for Polymer Synthesis" (published by Takayuki Otsu, published by Kagaku Dojin, 1st Edition, 1st edition, March 1, 1972) and the literature. And can be produced with reference to the references described in the above.

  Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, for example, by replacing oxygen with nitrogen to form a deoxygenated atmosphere, and while stirring, A method of heating and keeping the temperature is included. The polymerization initiator and the solvent used here are not particularly limited, and those commonly used in the art can be used. For example, as the polymerization initiator, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and the like) and organic peroxides (benzoyl peroxide and the like) Any solvent may be used as long as it can dissolve each monomer, and examples of the solvent (F) for the colored curable resin composition of the present invention include the solvents described below.

  The obtained copolymer may be used as it is after the reaction, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. A thing may be used. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during this polymerization, the solution after the reaction can be used as it is for the preparation of the colored curable resin composition of the present invention. Therefore, the production process of the colored curable resin composition of the present invention can be simplified.

In the resin [K2], the ratio of the structural units derived from each of the resins [K2] is defined as:
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 unit of the resin [K2] is in the above range, storage stability of the colored curable resin composition, developability when forming a colored pattern, and solvent resistance of the obtained color filter, It tends to have excellent heat resistance and mechanical strength.

  The resin [K2] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].

In the resin [K3], the ratio of the structural units derived from each of the resin [K3] is as follows:
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.
The resin [K3] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].

Resin [K4] obtains a copolymer of (a) and (c), and (b) has a cyclic ether having 2 to 4 carbon atoms and (a) has a carboxylic acid and / or carboxylic anhydride. Can be produced by adding
First, a copolymer of (a) and (c) is produced in the same manner as the method described as the method for producing the resin [K1]. In this case, it is preferable that the ratio of the structural units derived from each is the same as that of the resin [K3].

Next, the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer is partially reacted with the cyclic ether having 2 to 4 carbon atoms of (b).
Subsequent to the production of the copolymer of (a) and (c), the atmosphere in the flask was replaced with air from nitrogen, and (b), a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (for example, Tris ( A resin [K4] can be produced by putting a dimethylaminomethyl) phenol or the like) and a polymerization inhibitor (for example, hydroquinone) in a flask and reacting at 60 to 130 ° C. for 1 to 10 hours. it can.
(B) is preferably used in an amount of 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By setting the content in this range, the storage stability of the colored curable resin composition, the developability when forming a pattern, and the solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained pattern are well balanced. Tend. Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (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 based on 100 parts by mass of the total of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c).
The reaction conditions such as the charging method, the reaction temperature and the time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like. As in the case of 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.

As the resin [K5], as a first step, a copolymer of (b) and (c) is obtained in the same manner as in the method for producing the resin [K1] described above. Similarly to the above, the obtained copolymer may be used as it is after the reaction, as a concentrated or diluted solution, or as a solid (powder) by a method such as reprecipitation. You may use what was taken out as.
The ratio of the structural units derived from (b) and (c) is, with respect to the total mole number of all the structural units constituting the copolymer, 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.

Further, under the same conditions as in the method for producing the resin [K4], the carboxylic acid or carboxylic anhydride of (a) is added to the cyclic ether derived from (b) of the copolymer of (b) and (c). By reacting the product, resin [K5] can be obtained.
The amount of (a) used to react with the copolymer is preferably 5 to 80 mol per 100 mol of (b). Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferably used as (b) used in the resin [K5], and more preferably (b1-1).

Resin [K6] is a resin obtained by further reacting carboxylic anhydride with resin [K5].
A carboxylic anhydride is reacted with a hydroxy group generated by a reaction between a cyclic ether and a carboxylic acid or a carboxylic anhydride.
Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 , 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride and the like. The amount of the carboxylic anhydride to be used is preferably 0.5 to 1 mol per 1 mol of the (a) used.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] Resin [K1] such as decyl acrylate / (meth) acrylic acid copolymer; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) ) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- ( Resin [K2] such as (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; benzyl (meth) acrylate / Resins [K3] such as (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer; glycidyl (meth) acrylate was added to benzyl (meth) acrylate / (meth) acrylic acid copolymer Resin, tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer with glycidyl (meth) acrylate added, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acryl Resin [K4] such as resin obtained by adding glycidyl (meth) acrylate to acid copolymer; resin obtained by reacting (meth) acrylic acid with tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate copolymer , Tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resin [K5] such as resin obtained by reacting (meth) acrylic acid with copolymer; resin obtained by reacting (meth) acrylic acid with tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate copolymer Further, a resin [K6] such as a resin reacted with tetrahydrophthalic anhydride is exemplified.

The weight average molecular weight in terms of polystyrene of the resin (B) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, and still more preferably from 5,000 to 30,000. . When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film ratio 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 molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably from 1.1 to 6, and more preferably from 1.2 to 4.

  The acid value of the resin (B) is preferably from 50 to 170 mg-KOH / g, more preferably from 60 to 150, and still more preferably from 70 to 135 mg-KOH / g. 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 solution of potassium hydroxide.

  The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass, based on the total amount of the solid content. 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 ratio tend to be improved.

<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), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond and the like. Is a (meth) acrylate compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound 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 glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-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, etc. Is mentioned.
Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferred.

  The weight average molecular weight of the polymerizable compound (C) is preferably from 150 to 2,900, more preferably from 250 to 1,500.

  The content of the polymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, and still more preferably from 17 to 55% by mass, based on the total amount of solids. is there. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming a colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>
The polymerization initiator (D) is a compound that generates an active radical, an acid, or the like by the action of light or heat and can initiate polymerization, and is an oxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a biimidazole compound. And the like. The polymerization initiator (D) preferably contains at least one selected from the group consisting of an oxime compound, an alkylphenone compound and a biimidazole compound, and more preferably contains an oxime compound.

  Examples of the oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one. -2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methyl Benzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxa) Cyclopentanylmethyloxy) benzoyl {-9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl- -(2-Methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (all manufactured by BASF) and N-1919 (ADEKA) may be used. The oxime compound is preferably an O-acyl oxime compound. Above all, oxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-. At least one selected from the group consisting of 2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferable, and N-benzoyloxy-1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred. When these oxime compounds are used, a color filter with high brightness tends to be obtained.

Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane- Α-aminoalkylphenone compounds such as 1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one; 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-di Butoxy acetophenone, include α- hydroxyalkylphenone compounds such as benzyl dimethyl ketal, Irgacure (registered trademark) 369,907,379 (or, BASF Corp.) may be a commercially available product such as. The alkylphenone compound is preferably an α-aminoalkylphenone compound.

  As the triazine compound, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl)- 1,3,5-triazine, 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-methyl) Phenyl) ethenyl 1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and Irgacure (registered trademark) 819 (manufactured by BASF). May be used.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4 , 4 ', 5,5'-tetraphenylbiimidazole (for example, see 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 (trialkoxy) Phenyl) biimidazole (for example, see JP-B-48-38403 and JP-A-62-174204), wherein the phenyl group at the 4,4'5,5'-position is substituted by a carboalkoxy group. And imidazole compounds (for example, see JP-A-7-10913).

  Still other compounds 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, and 4-benzoyl-4'-. Benzophenone compounds such as methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethylanthraquinone And quinone compounds such as camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like. These are preferably used in combination with a polymerization initiation assistant (E) (especially amines) described later.

When two or more compounds are contained in the polymerization initiator (D), the combination thereof includes an oxime compound and an alkylphenone compound, an oxime compound and a triazine compound, an oxime compound and an acylphosphine oxide compound, an oxime compound and a biimidazole compound, Oxime compounds, alkylphenone compounds, biimidazole compounds, and the like.
Among them, the polymerization initiator (D) preferably contains an oxime compound and at least one selected from the group consisting of an alkylphenone compound and a biimidazole compound, and more preferably contains an oxime compound and an alkylphenone compound. . When both are included, the sensitivity at the time of manufacturing the color filter, the hardness of the color filter, and the chemical resistance tend to be excellent.

  The content of the polymerization initiator (D) is preferably from 1 to 400.1 to 30 parts by mass, more preferably from 1 to 40 parts by mass, based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). To 301 to 20 parts by mass, more preferably 3 to 20 parts by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, so that the productivity of the color filter is improved.

<Polymerization assistant (E)>
The polymerization initiation aid (E) is a compound or a sensitizer used to promote the polymerization of the polymerizable compound whose polymerization has been initiated by the polymerization initiator. When the polymerization initiator (E) is contained, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiator (E) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound.

  Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis ( Ethylmethylamino) benzophenone and the like, among which 4,4′-bis (diethylamino) benzophenone is preferable. A commercially available product such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may be used.

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene and the like can be mentioned.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, Examples include N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

  When these polymerization initiation aids (E) are used, the content thereof is preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Preferably it is 1 to 20 parts by mass. When the amount of the polymerization initiation aid (E) is within this range, a color filter can be formed with higher sensitivity, so that the productivity of the color filter tends to be improved.

<Solvent (F)>
The solvent (F) is not particularly limited, and a solvent usually used in the art can be used. For example, an ester solvent (a solvent containing -COO- in the molecule but not containing -O-), an ether solvent (a solvent containing -O- in the molecule but not containing -COO-), and an ether ester solvent (a solvent containing -COO- in the molecule) , A solvent containing -COO- and -O-), a ketone solvent (a solvent containing -CO- in the molecule and not containing -COO-), an alcohol solvent (containing OH in the molecule, -O-,- Solvents that do not contain CO— and —COO—), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

  Examples of the ester solvent 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, and butyl butyrate. , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.

  Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol 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, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, and the like phenetol and methyl anisole.

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and 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 and diethylene glycol monobutyl ether acetate.

  Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone. And the like.

  Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

  Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and mesitylene.

  Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

Among the above-mentioned solvents, an organic solvent having a boiling point of 120 ° C. or more and 180 ° C. or less at 1 atm is preferable from the viewpoint of coating properties and drying properties. As a solvent, 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-2-pentanone And N, N-dimethylformamide are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethyl lactate and ethyl 3-ethoxypropionate are more preferred.
The solvent (F) is preferably used by mixing two or more of these solvents.

  The content of the solvent (F) is preferably from 70 to 95% by mass, more preferably from 75 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention. In other words, the total amount of the solid content of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (F) is within the above range, the flatness at the time of coating is good, and the display characteristics tend to be good because the color density is not insufficient when a color filter is formed. .

<Leveling agent (G)>
Examples of the leveling agent (G) include a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone-based surfactant include a surfactant having a siloxane bond in a molecule. Specifically, Toray silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by 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, TSF-4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan GK). No.

  Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in a molecule. Specifically, Florad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and F554 R30, RS-718-K (manufactured by DIC Corporation), EFTOP (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals, Inc.), Surflon (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).

  Examples of the silicone surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples include Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

  The content of the leveling agent (G) is preferably from 0.001% by mass to 0.2% by mass, and more preferably from 0.002% by mass to 0.1% by mass, based on the total amount of the colored curable resin composition. %, More preferably 0.01 to 0.05% by mass. This content does not include the content of the pigment dispersant. When the content of the leveling agent (G) is within the above range, the flatness of the color filter can be improved.

<Antioxidant (J)>
Examples of the antioxidant (J) include a phenolic antioxidant, an amine-based antioxidant, a phosphorus-based antioxidant and a sulfur-based antioxidant, and a phenol-based antioxidant and a phosphorus-based antioxidant are preferred.

  The phenolic antioxidant is an antioxidant having a phenolic hydroxy group in the molecule, and preferably has an alkyl group branched at the ortho position of the phenolic hydroxy group. In the present specification, an antioxidant having both a phenolic hydroxy group and a phosphate or phosphite structure is classified as a phosphorus-based antioxidant.

  Examples of the phenolic antioxidant include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4,4′-butylidene-bis (3-methyl-6- tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2-tert-butyl-6- (3-tert -Butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, (tetrakis [methylene-3- (3,5-di-tet-butyl-4-hydroxyphenyl) propionate] methane, pentaerythritol tetrakis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene -2,4,6-triyl) tri-p-cresol, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4 , 6 (1H, 3H, 5H) -trione, 1,3,5-tris ((4-tert-butyl-3-hydroxy-2,6-xylyl) methyl) -1,3,5-triazine-2, 4,6 (1H, 3H, 5H) -trione, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], benzenepropanoic acid, 3,5-bis (1, 1-dimethylethyl) -4-h Roxy, C7-C9 side chain alkyl ester, 4,6-bis (octylthiomethyl) -o-cresol, Irganox® 3125 (manufactured by BASF), 2,4-bis (n-octylthio) -6 (4-hydroxy 3 ′, 5′-di-tert-butylanilino) -1,3,5-triazine, 3,9-bis (2- (3- (3-tert-butyl-4-hydroxy-5-methyl Phenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, Sumilizer (registered trademark) BHT (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer (registered) Trademark) GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer (registered trademark) GS (manufactured by Sumitomo Chemical Co., Ltd.), and Cyanox (registered trademark) 1790 (Cytec Co., Ltd.) ) And made of vitamin E (Eisai Co., Ltd.), and the like.

The amine antioxidant is an antioxidant having an amino group in the molecule.
Examples of the amine antioxidant include 1-naphthylamine, phenyl-1-naphthylamine, p-octylphenyl-1-naphthylamine, p-nonylphenyl-1-naphthylamine, p-dodecylphenyl-1-naphthylamine, and phenyl-2. A naphthylamine-based antioxidant such as naphthylamine; N, N'-diisopropyl-p-phenylenediamine, N, N'-diisobutyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N ' -Di-β-naphthyl-p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine, N-cyclohexyl-N′-phenyl-p-phenylenediamine, N-1,3-dimethylbutyl-N '-Phenyl-p-phenylenediamine, dioctyl-p-phenyl Phenylenediamine antioxidants such as diamine, phenylhexyl-p-phenylenediamine and phenyloctyl-p-phenylenediamine; dipyridylamine, diphenylamine, p, p'-di-n-butyldiphenylamine, p, p'-di- tert-butyldiphenylamine, p, p′-di-tert-pentyldiphenylamine, p, p′-dioctyldiphenylamine, p, p′-dinonyldiphenylamine, p, p′-didecyldiphenylamine, p, p′-didodecyl Diphenylamine-based oxidation such as diphenylamine, p, p'-distyryldiphenylamine, p, p'-dimethoxydiphenylamine, 4,4'-bis (4-α, α-dimethylbenzoyl) diphenylamine, p-isopropoxydiphenylamine, dipyridylamine Inhibitor Phenothiazine-based antioxidants such as phenothiazine, N-methylphenothiazine, N-ethylphenothiazine, 3,7-dioctylphenothiazine, phenothiazine carboxylate, and phenoselenazine;

The phosphorus-based antioxidant is an antioxidant having a phosphate ester structure or a phosphite ester structure.
Examples of the phosphorus-based antioxidant include 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphepin, tris (2,4-di-tert-butylphenyl) phosphite, diphenylisooctylphosphite, 2,2′-methylenebis (4,6-di- (tert-butylphenyl) octylphosphite, diphenylisodecylphosphite, diphenylisodecylphosphite, triphenylphosphate, tributylphosphate, distearylpentaerythritol diphosphite, cyclic neopentanetetraylbis (2,6- Di-tert-butyl-4-methylphenyl) Phosphite, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butylbenzo [d, f] [1,3 2] dioxaphosphepin, tris (nonylphenyl) phosphite, tris (mono- & dinonylphenyl mixed) phosphite, diphenylmono (tridecyl) phosphite, 2,2′-ethylidenebis (4,6- Di-tert-butylphenol) fluorophosphite, phenyldiisodecylphosphite, tris (2-ethylhexyl) phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) ) -4,4'-Biphenylene-di-phosph Onitite, 4,4'-isopropylidenediphenyltetraalkyl (C12-C15) diphosphite, 4,4'-butylidenebis (3-methyl-6-tert-butylphenyl) -ditridecylphosphite, bis (nonylphenyl) Pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-diphosphite, cyclic neopentanetetraylbis (2,6-di-tert-butyl-4-methylphenyl- Phosphite), 1,1,3-tris (2-methyl-4-ditridecylphosphite-5-tert-butylphenyl) butane, tetrakis (2,4-di-tert-butyl-5-methylphenyl)- 4,4'-biphenylenediphosphonite, tri-2-ethylhexene Silphosphite, triisodecyl phosphite, tristearyl phosphite, phenyl diisodecyl phosphite, trilauryl trithiophosphite, distearyl pentaerythritol diphosphite, tris (nonylate phenyl) phosphite tris [2-[[2 , 4,8,10-Tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine, bis (2,4-bis (1, 1-dimethylethyl) -6-methylphenyl) ethyl ester phosphite, ADEKA STAB (registered trademark) 329K (manufactured by ADEKA Corporation), ADEKA STAB (registered trademark) PEP36 (manufactured by ADEKA Corporation), ADK STAB (registered trademark) PEP-8 (made by ADEKA Corporation), Sandst b (registered trademark) P-EPQ (made by Clariant), Weston (registered trademark) 618 (made by GE), Weston (registered trademark) 619G (made by GE), Ultranox (registered trademark) 626 (made by GE) , 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] Dioxaphosphepin) and the like.

The sulfur-based antioxidant is an antioxidant having a sulfur atom in a molecule.
Examples of the sulfur-based antioxidant include β-alkylmercaptopropionic acid of dilauryl thiodipropionate, dialkylthiodipropionate compounds such as dimyristyl and distearyl, and polyols such as tetrakis [methylene (3-dodecylthio) propionate] methane Ester compounds and the like.

  When the colored curable resin composition of the present invention contains an antioxidant (J), its content is preferably 0.05 to 10% by mass, more preferably 0.1 to 10% by mass, based on the total amount of solids. The content is 1 to 8% by mass, and more preferably 0.2 to 7% by mass. When the content of the antioxidant (J) is within the above range, the obtained color filter is preferable because deterioration of color characteristics is further suppressed.

<Thiol compound (T)>
The thiol compound (T) is a compound having a sulfanyl group in the molecule.
Specific examples of the thiol compound (T) include, for example, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, triglycol Methylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl Tristhiopropionate, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) buta , Dipentaerythritol hexakisthiopropionate, dipentaerythritol hexakis (3-mercaptobutyrate), 1,3,5-trismercaptopropionate-1,3,5-triazine-2,4,6 ( 1H, 3H, 5H) -trione, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like. No.
When the colored curable resin composition of the present invention contains a thiol compound (T), its content is preferably from 2 to 70 parts by mass based on 100 parts by mass of the polymerization initiator (D). , More preferably 5 to 50 parts by mass. When the content of the thiol compound (T) is in the above range, the sensitivity tends to be high, and the developability tends to be good.

<Other ingredients>
The colored curable resin composition of the present invention may contain, if necessary, additives known in the art, such as a filler, another polymer compound, an adhesion promoter, a light stabilizer, and a chain transfer agent. .

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention includes, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (F) used as needed. It can be prepared by mixing a leveling agent (G), a polymerization initiation assistant (E), an antioxidant (J), a thiol compound (T) and other components.
It is preferable that the pigment is previously mixed with part or all of the solvent (F) and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, if necessary, a part or all of the pigment dispersant and the resin (B) may be blended. The desired colored curable resin composition can be prepared by mixing the remaining components into the pigment dispersion obtained in this manner so as to have a predetermined concentration.
The xanthene dye (A1), the cyanine dye (A2) and the dye (A4) may be previously dissolved in a part or all of the solvent (F) to prepare a solution. When the solution is prepared, it is preferable to filter the solution with a filter having a pore size of about 0.01 to 1 μm.
It is preferable to filter the colored curable resin composition after mixing with a filter having a pore size of about 0.1 to 10 μm.

<Production method of color filter>
A color filter formed from the colored curable resin composition of the present invention is also one of the present invention. Examples of the color filter of the present invention include a colored pattern (that is, a coating film having a resolved pattern) and a colored coating film.
Examples of a method for producing the colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, a printing method, and the like. Among them, the photolithographic method is preferred. The photolithographic method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, exposed to light through a photomask, and developed. In the photolithographic method, a colored coating film which is a cured product of the coloring composition layer can be formed by not using a photomask at the time of exposure and / or not developing. The colored pattern and the colored coating film thus formed are the color filters of the present invention.
The thickness of the color filter to be produced is not particularly limited and can be appropriately adjusted depending on the purpose and application, and is usually 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 20 μm. ６6 μm.

  Examples of the substrate include quartz glass, borosilicate glass, alumina silicate glass, a glass plate such as soda lime glass having a silica-coated surface, a resin plate such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, silicon, and the like. On which an aluminum, silver, silver / copper / palladium alloy thin film or the like is formed. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

The formation of the color filter by the photolithographic method can be performed by a known or commonly used device or condition. For example, it can be manufactured as follows.
First, a colored curable resin composition is applied on a substrate, dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent and dried to obtain a smooth colored composition layer.
Examples of the coating method include a spin coating method, a slit coating method, a slit and spin coating method, and the like.
The temperature in the case of performing heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. The heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.
When performing drying under reduced pressure, it is preferable to perform drying under a pressure of 50 to 150 Pa in a temperature range of 20 to 25 ° C.
The thickness of the coloring composition layer is not particularly limited, and may be appropriately selected depending on the intended thickness of the color filter.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
As a light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, and light of about 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specifically, mercury lamps, light emitting diodes, metal halide lamps, halogen lamps and the like can be mentioned.
The entire exposure surface may be uniformly irradiated with parallel rays, and accurate alignment between the photomask and the substrate on which the coloring composition layer is formed can be performed. Therefore, an exposure apparatus such as a mask aligner and a stepper can be used. It is preferred to use.

A pattern is formed on the substrate by developing the exposed colored composition layer by contacting it with a developer. By the development, the unexposed portions of the colored composition layer are dissolved in the developer and removed.
As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide or the like is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of a paddle method, a dipping method, a spray method and the like. Further, the substrate may be inclined at an arbitrary angle during development.
After development, it is preferable to wash with water.

  Further, it is preferable to perform post-baking on the obtained colored pattern. The postbake temperature is preferably from 150 to 250C, more preferably from 160 to 235C. The post-bake time is preferably from 1 to 120 minutes, more preferably from 10 to 60 minutes.

  According to the colored curable resin composition of the present invention, a color filter having few defects can be produced because the developability during the production of the color filter is excellent, and the yield of the color filter tends to be improved. The color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, or the like) and a solid-state imaging device.

Hereinafter, the colored curable resin composition of the present invention will be described in more detail with reference to examples.
"%" And "parts" in the examples are% by mass and parts by mass unless otherwise specified.

[Synthesis Example 1]
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at a rate of 0.02 L / min to form a nitrogen atmosphere, and 220 parts of ethyl lactate was charged and heated to 70 ° C. with stirring. Next, a mixed solution of 84 parts of methacrylic acid, 336 parts of a mixture of 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decane-8 or / and 9-yl acrylate, and 140 parts of ethyl lactate, The solution was dropped into a flask kept at 70 ° C. over 4 hours using a dropping funnel. On the other hand, a solution in which 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 95 parts of ethyl lactate was dropped into the flask over another 4 hours using another dropping funnel. After the dropping of the polymerization initiator solution was completed, the temperature was maintained at 70 ° C. for 4 hours, and then cooled to room temperature to obtain a copolymer solution having a solid content of 48%. The weight average molecular weight of the copolymer (resin B1) was 8.0 × 10 ³ , the molecular weight distribution was 2.5, and the acid value of the solid was 104 mg-KOH / g.
Resin B1 has the following structural units.

[Synthesis Example 2]
182 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube, and the atmosphere in the flask was changed from air to nitrogen. The temperature was raised to 100 ° C., and 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, and monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) 22 A solution obtained by adding 3.6 g of 2,2′-azobisisobutyronitrile to a mixture consisting of 0.0 g (0.10 mol) and 136 g of propylene glycol monomethyl ether acetate was dropped into the flask, and further stirred at 100 ° C. Continued. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 mol (50 mol% based on the carboxy group of methacrylic acid used in the reaction)] was added. 9 g and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. to obtain a copolymer solution having a solid content of 35%.
The weight average molecular weight of the copolymer (resin B2) was 3.0 × 10 ⁴ , and the acid value of the solid content was 79 mg-KOH / g. Resin B2 has the following structural units.

[Synthesis Example 3]
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at a rate of 0.02 L / min to form a nitrogen atmosphere, 305 parts of ethyl lactate was added, and the mixture was heated to 100 ° C. with stirring. Next, a mixed solution of 90 parts of methacrylic acid, 210 parts of benzyl methacrylate and 140 parts of ethyl lactate was dropped into the flask kept at 100 ° C. over 4 hours using a dropping funnel. On the other hand, a solution prepared by dissolving 30 parts of polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts of ethyl lactate was dropped into the flask over another 4 hours using another dropping funnel. After the dropping of the polymerization initiator solution was completed, the temperature was maintained at 100 ° C. for 4 hours, and then cooled to room temperature to obtain a copolymer solution having a solid content of 30%. The weight average molecular weight of the copolymer (resin B3) was 1.2 × 10 ⁴ , the molecular weight distribution was 2.2, and the acid value of the solid content was 154 mg-KOH / g. Resin B3 has the following structural units.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin was performed using the GPC method under the following conditions.
Apparatus: K2479 (manufactured by Shimadzu Corporation)
Column: SHIMADZU Shim-pack GPC-80M
Column temperature; 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector; RI
Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio of the weight average molecular weight and the number average molecular weight in terms of polystyrene (Mw / Mn) obtained above was defined as the molecular weight distribution.

[Synthesis Example 4]
A solution (Ss-1) was prepared by dissolving 0.06 part of the compound represented by the formula (S-1) in 1,000 parts of ion-exchanged water at room temperature.

  Separately, C.I. I. A solution (Ss-2) was prepared by dissolving 0.03 parts of Acid Red 52 in 50 parts of ion-exchanged water at room temperature. The solution (Ss-2) was added dropwise to the solution (Ss-1) over 1 hour at room temperature, and then stirred for 24 hours. The resulting precipitate is obtained by suction filtration, and the precipitate is washed twice with 100 parts of ion-exchanged water, and then dried under reduced pressure at 60 ° C. to give the compound represented by the formula (S-2) in 0.1. One copy was obtained.

Examples 1 to 10 and Comparative Example 1
<Preparation of pigment dispersion liquid 1>
C. I. Pigment Blue 15: 6 (pigment) 25 parts Acrylic pigment dispersant 8.4 parts and propylene glycol monomethyl ether acetate 81 parts are mixed, and the pigment is sufficiently dispersed using a bead mill to obtain Pigment Dispersion Liquid 1. Was.
<Preparation of colored curable resin composition>
The components shown in Table 1 were mixed to obtain a colored curable resin composition.

In Table 1, the resin (B) represents the content (part) in terms of solid content.
Colorant (A)
A1-1: A mixture of compounds represented by formulas (1-1) to (1-8) (synthesized by the method described in JP 2010- 211198 A, R ⁴⁰ is a 2-ethylhexyl group) (JP 2010) Synthesized by the method described in JP-A-212198)
A1-2: Compound represented by formula (1-32) (synthesized by the method described in JP 2013-64096 A)
A1-3; I. Acid Red 52
A2-1: Compound represented by the following formula (NK-8635; manufactured by Hayashibara Biochemical Laboratory)

Polymerizable compound (C)
C1: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd .; KAYARAD (registered trademark) DPHA)
C2: Monoesterified product of dipentaerythritol pentaacrylate and succinic acid, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (TO-1382; manufactured by Toagosei Co., Ltd.)
Polymerization initiator (D)
D1: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF; oxime compound)
D2; 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (Irgacure (registered trademark) 369; manufactured by BASF; alkylphenone compound) D3; 2-methyl-2-morpholino- 1- (4-methylsulfanylphenyl) propan-1-one (Irgacure (registered trademark) 907; manufactured by BASF; alkylphenone compound)
D4; a mixture of compounds represented by the following formula (CHEMCURE-TCDM; manufactured by Cambridge; biimidazole compound)

Polymerization initiation aid (E)
E1; 2,4-diethylthioxanthone (KAYACURE (registered trademark) DETX-S; Nippon Kayaku Co., Ltd .; thioxanthone compound)
Leveling agent (G); polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Dow Corning Toray)
Solvent (F)
F1: propylene glycol monomethyl ether acetate F2; propylene glycol monomethyl ether F3; ethyl lactate F4; 4-hydroxy-4-methyl-2-pentanone

Examples 11 to 17
<Preparation of pigment dispersion 2>
C. I. Pigment Blue 15: 6 (pigment) 25 parts Acrylic pigment dispersant 8.4 parts, and propylene glycol monomethyl ether acetate 181 parts are mixed, and the pigment is sufficiently dispersed using a bead mill. Obtained.

<Preparation of colored curable resin composition>
The components shown in Table 2 were mixed to obtain a colored curable resin composition.

A-1; compound represented by formula (S-2) A4-1; compound represented by formula (AI-a10) (synthesized by the method described in JP-A-2015-28121)

  A4-2; Compound represented by formula (AIla16) (synthesized by the method described in JP-A-2015-28121)

A4-3; I. Solvent Blue 45
B1, C1, D1, D2, D3, D4, E1; same as each component described in Table 1 J1; 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2 , 4,8,10-Tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphepin (Sumilyzer (registered trademark) GP; manufactured by Sumitomo Chemical Co., Ltd.)
T1; pentaerythritol tetrakis (3-sulfanylpropionate) (PEMP; manufactured by SC Organic Chemicals Inc.)
Leveling agent (G), F1, F2, F3, F4; same as each component described in Table 1

<Preparation of color filter>
A colored curable resin composition was applied on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated) by spin coating, and then prebaked at 100 ° C. for 3 minutes to form a colored composition layer. After cooling, the distance between the glass substrate on which the coloring composition layer was formed and the quartz glass photomask was set to 100 μm, and exposed to light (TME-150RSK; manufactured by Topcon Corporation) in an air atmosphere at 150 mJ / cm ^2. At a light exposure of 365 nm (based on 365 nm). A photomask on which a 100 μm line and space pattern was formed was used. The glass substrate on which the colored composition layer after light irradiation is formed is immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds, and washed with water. Thereafter, post baking was performed in an oven at 220 ° C. for 20 minutes to obtain a color filter.

<Film thickness measurement>
The film thickness of the obtained color filter was measured by a film thickness measuring device (DEKTAK3; manufactured by Japan Vacuum Engineering Co., Ltd.). The results are shown in Tables 3 and 4.

<Chromaticity evaluation>
The spectrum of the obtained color filter is measured by a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity coordinates (x , Y) and the tristimulus value Y were measured. The higher the value of Y, the higher the brightness. The results are shown in Tables 3 and 4.

<Evaluation of residue during development>
A colored curable resin composition was applied on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated) by spin coating, and then prebaked at 100 ° C. for 3 minutes to form a colored composition layer. After cooling, the glass substrate on which the coloring composition layer is formed is developed by immersing it in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds. After that, washing was carried out sufficiently. A 3 cm square portion of the center of the glass substrate was rubbed with a cotton swab, and it was confirmed whether coloring was observed on the cotton swab.
When no color was observed on the swab, it was judged that there was no residue generated during the development (hereinafter, this residue is referred to as “development residue”), and evaluated as ○ (= good). When coloring was observed on the swab, it was judged that there was a development residue, and evaluated as x (bad). The results are shown in Tables 3 and 4.

  ADVANTAGE OF THE INVENTION According to the colored curable resin composition of this invention, when producing a color filter, a residue can be reduced.

Claims (5)

Contains colorant, resin, polymerizable compound and polymerization initiator,
Colorants, xanthene dyes, or colorants including cyanine dyes and blue pigments, or Ri colorants der containing salt and blue pigments and cations derived from anionic cyanine compound derived from the xanthene compound,
Polymerization initiator, a polymerization initiator der Ru colored curable resin composition comprising at least oxime compound. Polymerization initiator, further alkylphenone compounds and colored curable resin composition according to claim 1, wherein the polymerization initiator comprising at least one compound selected from the group consisting of biimidazole compounds. Further, a blue or violet dye, unlike the dyes of the xanthene dyes and cyanine dyes, and claim 1 or 2 including a different dye than the salt of a cation derived from an anionic cyanine compound derived from the xanthene compound The colored curable resin composition according to the above. A color filter formed from the colored curable resin composition according to any of claims 1-3. A display device comprising the color filter according to claim 4 .