TWI670268B - Compound - Google Patents

Abstract

An object of the present invention is to provide a coloring resin composition that is easy to synthesize a coloring agent and can form a color filter in which the sublimation of the coloring agent is suppressed.

The compound of the present invention is represented by formula (I).

Description

Compound

The present invention relates to a compound or the like usable as a dye (for example, a colored resin composition, a color filter, a liquid crystal display device).

Dyes are used, for example, to perform color display using reflected light or transmitted light in the fields of fiber materials, liquid crystal display devices, inkjet, and the like. As this dye, coumarin 6 is known (Patent Document 1).

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2006-154740 (Embodiment 8)

An object of the present invention is to provide a coloring resin composition that is easy to synthesize a coloring agent and can form a color filter in which the sublimation of the coloring agent is suppressed.

The present invention includes the following inventions.

[1] a compound represented by formula (I), [Chem. 1]

[In formula (I), X represents an oxygen atom or a sulfur atom; R ¹ and R ² each independently represent a hydrocarbon group having 1 to 20 carbon atoms; n represents an integer of 1 to 4; A represents -SO ₂ -L ¹ -OM; M represents a hydrogen atom or an alkali metal atom; when a plurality of M are present, they may be the same or different from each other; L ¹ represents a divalent hydrocarbon group having 1 to 60 carbon atoms; -CH = which constitutes the divalent hydrocarbon group may be Substituting -N =, -CH ₂ -constituting the divalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ³ )-, a sulfonyl group, or a carbonyl group. The hydrogen atom contained in the divalent hydrocarbon group may be Is substituted with a halogen atom, cyano, nitro, carbamoyl, sulfamoyl, -SO ₃ M ³ , -CO ₂ M ³ , hydroxyl, formyl or amine; R ³ represents a hydrogen atom, carbon A monovalent hydrocarbon group of 1 to 20 or a group represented by formula (z); a hydrogen atom contained in the monovalent hydrocarbon group may be substituted with a halogen atom, a hydroxyl group, or a carboxyl group, and -CH ₂ -constituting the monovalent hydrocarbon group may be replaced by Substituted with a carbonyl group; when a plurality of R ³ are present, they may be the same as or different from each other;

In formula (z), L ²² and L ³³ each independently represent a divalent hydrocarbon group having 1 to 30 carbon atoms; -CH = constituting the divalent hydrocarbon group may be substituted with -N =, and -CH ₂ -constituting the divalent hydrocarbon group It may be substituted with an oxygen atom, a sulfur atom, -N (R ⁴⁴ )-, a sulfonyl group, or a carbonyl group, and a hydrogen atom contained in the divalent hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, or a carbamate group. , Sulfamoyl, -SO ₃ M ³ , -CO ₂ M ³ , hydroxyl, formamyl, or amine; M ¹ represents a hydrogen atom or an alkali metal atom; in the case where a plurality of M ¹ are present, they and each other may be the same or different; substituents L ^1, -SO ^₃ M ₃ or -CO ₂ M ³ hydrogen atoms contained in L ²² or L ³³ of the divalent hydrocarbon group contained in the M ³ represents a hydrogen atom or an alkali metal atom; in the presence of In the case of a plurality of M ³ , they may be the same or different from each other; R ⁴⁴ represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbons; in the case of a plurality of R ⁴⁴ , they may be the same or different from each other] .

[2] The compound according to [1], wherein the A is -SO ₂ -OL ^a -OM, -SO ₂ -NR ³ -L ^b -OM, or -SO ₂ -NR ³ -L ² -OCO-L ³ -CO-OM, [wherein R ³ and M each have the same meaning as above; L ^a and L ^b are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, and -CH ₂ -which constitutes the divalent hydrocarbon group may be Is substituted with an oxygen atom or a carbonyl group; a hydrogen atom contained in the divalent hydrocarbon group may be substituted with a halogen atom or a carboxyl group; L ² and L ³ each independently represent a divalent hydrocarbon group having 1 to 30 carbon atoms; -CH = may be substituted with -N =, and -CH ₂ -constituting the divalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ⁵⁵ )-, a sulfonyl group, or a carbonyl group. The hydrogen atom contained may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, an sulfamoyl group, -SO ₃ M ³ , -CO ₂ M ³ , a hydroxyl group, a formyl group, or an amine group; M ³ Represents the same meaning as above; in the case where a plurality of M ³ are present, they may be the same or different from each other; R ⁵⁵ represents a hydrogen atom or a monovalent hydrocarbon group having a carbon number of 1 to 20; when a plurality of R ⁵⁵ are present , They may be the same or different from each other].

[3] The compound according to [2], wherein each of L ^a and L ^{b is} independently a phenylene group, a methylene group, an ethylidene group, a methylethylidene group, or a propylidene group.

[4] The compound according to [1], [2] or [3], which is represented by formula (II),

[In formula (II), n, X, R ¹ , R ² , L ² and L ^{3 have} the same meanings as above; R ³³ represents a hydrogen atom or -L ²² -OCO-L ³³ -CO ₂ M ² ; L ²² and L ³³ each have the same meaning as described above; M ² represents a hydrogen atom or an alkali metal atom; and when a plurality of M ² are present, they may be the same or different from each other].

[5] The compound according to [1] or [4], wherein the L ²² is a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the L ³³ is a divalent aliphatic hydrocarbon group which may be substituted by a carboxyl group or a halogen atom. Or an aromatic hydrocarbon group.

[6] The compound according to any one of [2] to [4], wherein the L ² is a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the L ³ is 2 which may be substituted by a carboxyl group or a halogen atom. Valence aliphatic hydrocarbon group or aromatic hydrocarbon group.

[7] The compound according to any one of [1] to [6], wherein R ¹ and R ² are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[8] A coloring resin composition containing a coloring agent containing the compound according to any one of [1] to [7], a resin, a polymerizable compound, a polymerization initiator, and a solvent.

[9] A color filter formed from the colored resin composition according to [8].

[10] A liquid crystal display device including the color filter according to [9].

According to the present invention, it is possible to provide a coloring resin composition in which a colorant can be easily synthesized and a color filter capable of suppressing sublimation of the colorant can be formed.

The compound of the present invention is a compound represented by formula (I), and may also be a compound represented by formula (II) (hereinafter sometimes referred to as compound (I) and compound (II)). The compounds of the present invention also include tautomers or salts thereof.

[In formula (I), X represents an oxygen atom or a sulfur atom.

R ¹ and R ² each independently represent a hydrocarbon group having 1 to 20 carbon atoms.

n represents an integer from 1 to 4.

A represents -SO ₂ -L ¹ -OM.

M represents a hydrogen atom or an alkali metal atom. When there are a plurality of Ms, they may be the same or different from each other.

L ¹ represents a divalent hydrocarbon group having 1 to 60 carbon atoms. -CH = constituting the divalent hydrocarbon group may be substituted with -N =, and -CH ₂ -constituting the divalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ³ )-, a sulfonyl group, or a carbonyl group The hydrogen atom contained in the divalent hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M ³ , -CO ₂ M ³ , a hydroxyl group, and a methyl group Or amine.

R ³ represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a group represented by formula (z). A hydrogen atom contained in the monovalent hydrocarbon group may be substituted with a halogen atom, a hydroxyl group, or a carboxyl group, and -CH ₂ -constituting the monovalent hydrocarbon group may be substituted with a carbonyl group.

When a plurality of R ³ are present, they may be the same as or different from each other.

In formula (z), L ²² and L ³³ each independently represent a divalent hydrocarbon group having 1 to 30 carbon atoms. -CH = constituting a divalent hydrocarbon group may be substituted with -N =, -CH ₂ -constituting the divalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ⁴⁴ )-, a sulfonyl group, or a carbonyl group, The hydrogen atom contained in the divalent hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, an sulfamoyl group, -SO ₃ M ³ , -CO ₂ M ³ , a hydroxyl group, a formyl group, or Amine.

M ¹ represents a hydrogen atom or an alkali metal atom. When a plurality of M ¹ exist, they may be the same as or different from each other.

Substituent L ^1, -SO hydrogen atom of L ²² or L ³³ of the divalent hydrocarbon group contained in _{it. 3} or -CO ₂ M ³ M ³ M ³ contained in the hydrogen atom or alkali metal atom. When there are a plurality of M ³ , they may be the same or different from each other.

R ⁴⁴ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. In the case of a plurality of R ⁴⁴ , they may be the same or different from each other]

[In formula (II), n, X, R ¹ , R ² , L ² and L ³ each have the same meaning as described above.

R ³³ represents a hydrogen atom or -L ²² -OCO-L ³³ -CO ₂ M ² .

L ²² and L ³³ each have the same meaning as described above.

M ² represents a hydrogen atom or an alkali metal atom. In the case of a plurality of M ² , they may be the same or different from each other]

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in R ¹ and R ² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, and third butyl. Base, (2-ethyl) butyl, pentyl, isopentyl, 3-pentyl, neopentyl, third pentyl, 1-methylpentyl, 2-methylpentyl, (3-ethyl ) Pentyl, hexyl, isohexyl, 5-methylhexyl, (2-ethyl) hexyl, heptyl, (3-ethyl) heptyl, octyl, nonyl, decyl, undecyl, Saturated aliphatic hydrocarbon groups such as dodecyl, octadecyl, isopropenyl, 1-propenyl, 2-propenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, etc. Aliphatic hydrocarbon groups such as unsaturated aliphatic hydrocarbon groups; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1,2-dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 1,4-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4 -Dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2,2 -Dimethylcyclohexyl, 3,3-di Cyclohexyl, 4,4-dimethylcyclohexyl, 2,4,6-trimethylcyclohexyl, 2,2,6,6-tetramethylcyclohexyl, 3,3,5,5-tetramethyl Saturated alicyclic hydrocarbon groups such as cyclohexyl, unsaturated alicyclic hydrocarbon groups such as cyclohexenyl; phenyl, o-tolyl, m-tolyl, p-tolyl, 2,3-dimethylphenyl, 2,4 -Dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4 Aromatic hydrocarbon groups such as 1,6-trimethylphenyl, o-cumyl, m-cumyl, p-cumyl, 2,6-bis (2-propyl) phenyl, etc .; Examples include aralkyl groups such as benzyl, phenethyl, biphenyl, 1-naphthyl, and 2-naphthyl, and combinations thereof.

R ¹ and R ² are each preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms. The carbon number is more preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 3. The monovalent hydrocarbon group is more preferably a monovalent saturated or unsaturated aliphatic hydrocarbon group, and even more preferably a monovalent saturated aliphatic hydrocarbon group.

R ¹ and R ^{2 are} preferably methyl, ethyl, propyl, isopropyl, butyl, hexyl, (2-ethyl) hexyl and octyl, more preferably ethyl, butyl, hexyl, (2-ethyl) hexyl and octyl. When R ¹ and R ^{2 are} these groups, the compound represented by formula (I) or the compound represented by formula (II) is easily dissolved in a solvent.

X represents an oxygen atom or a sulfur atom.

n represents an integer from 1 to 4. n is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.

A represents -SO ₂ -L ¹ -OM. A is preferably -SO ₂ -OL ^a -OM, -SO ₂ -NR ³ -L ^b -OM, or -SO ₂ -NR ³ -L ² -OCO-L ³ -CO-OM.

L ¹ represents a divalent hydrocarbon group having 1 to 60 carbon atoms. L ^{1 is} preferably a divalent hydrocarbon group having 1 to 30 carbon atoms, and more preferably a divalent hydrocarbon group having 1 to 20 carbon atoms.

In L ¹ , the divalent hydrocarbon group may be methylene, ethylidene, propane-1,3-diyl (propylidene), propane-1,2-diyl (propylidene), butane-1 4,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1 , 9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, ten Tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl, octadecane-1,18 -Diyl, undecane-1,19-diyl, eicosane-1,20-diyl, tridecane-1,30-diyl, tetradecane-1,40-diyl, fifty Linear alkane diyl such as alkane-1,50-diyl, hexadecane-1,60-diyl, methyl-ethyl-1,2-diyl (methylethenyl), butane- 1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, 2-methylbutane- Aliphatic hydrocarbon groups such as branched alkanediyl groups such as 1,4-diyl, ethane-1,1-diyl, propane-1,1-diyl, and propane-2,2-diyl.

In L ¹ , the divalent hydrocarbon group may be a monocyclic or polycyclic alicyclic hydrocarbon group, and may be cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, or cyclohexane. -1,2-diyl, 1-methylcyclohexane-1,2-diyl, cyclohexane-1,4-diyl, cyclooctane-1,2-diyl, cyclooctane-1 , 5-diyl and other monocyclic naphthenic diyl, etc. Alkane-2,3-diyl Alkane-1,4-diyl, Polycyclic cycloalkanediyl and other alicyclics such as alkane-2,5-diyl, adamantane-1,2-diyl, adamantane-1,5-diyl, and adamantane-2,6-diyl Alkyl.

In L ¹ , the divalent hydrocarbon group may be a monocyclic or polycyclic aromatic hydrocarbon group, and may be a monocyclic aromatic hydrocarbon group such as a phenylene group, a naphthyl group, a biphenylene group, a bitriphenylene group, and the like. Alkyl.

In L ¹ , the above-mentioned divalent hydrocarbon group may be a combination of one or more selected from the group consisting of the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group.

In L ¹ , -CH = constituting the divalent hydrocarbon group may be substituted by -N =, and -CH ₂ -constituting the divalent hydrocarbon group may be substituted by oxygen atom, sulfur atom, -N (R ³ )-, A fluorenyl group or a carbonyl group, the hydrogen atom contained in the divalent hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, an sulfamoyl group, -SO ₃ M ³ , -CO ₂ M ³ , a hydroxyl group , Formamidine or amine.

Examples of the group represented by L ¹ include the groups represented by the formulas (L1-1) to (L1-43). ● represents a bond with a sulfur atom. ○ represents a bond with an oxygen atom.

[Chemical 8]

[Chemical 10]

[Chemical 11]

The base represented by L ¹ is preferably the base represented by formula (L1-9) to formula (L1-19) and formula (L1-25) to formula (L1-43), and more preferably formula (L1- 9) ~ Formula (L1-12), Formula (L1-14), Formula (L1-17) ~ Formula (L1-19) and Formula (L1-25) ~ Formula (L1-43), and further Formulas (L1-31) to (L1-34) are preferred. If the base represented by L ¹ is such a base, it is easy to synthesize. In addition, the aromatic ring system in the above chemical formula is exemplified as a compound having a bonding bond at the 1st and 4th positions, or the 1st and the 2nd positions, respectively. And 2-digit bond keys, 1- and 2-digit bond keys can be changed to 1- and 4-digit bond keys.

L ^a and L ^b are each preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, more preferably a carbon number of 1 to 20 selected from the group consisting of a divalent aromatic hydrocarbon group and a divalent saturated aliphatic hydrocarbon group. The hydrocarbyl group is more preferably a phenylene group, a methylene group, an ethylidene group, a methylethylidene group, or a propylidene group, and is more preferably a methylene group, an ethylidene group, or a methylidene group, and particularly preferably a methylidene group. Ethyl or methyl ethyl.

In L ^a and L ^b , —CH ₂ — constituting the divalent hydrocarbon group may be substituted with an oxygen atom or a carbonyl group. The hydrogen atom contained in the divalent hydrocarbon group may be substituted with a halogen atom or a carboxyl group.

L ² and L ³ each independently represent a divalent hydrocarbon group having 1 to 30 carbon atoms.

L ² and L ^{3 are,} for example, one or more of a saturated or unsaturated divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group having 1 to 30 carbon atoms, preferably a linear or branched chain having 1 to 20 carbon atoms. One or more of the bivalent aliphatic hydrocarbon group and aromatic hydrocarbon group in the shape, more preferably one or more of linear or branched divalent aliphatic hydrocarbon group and aromatic hydrocarbon group having 1 to 10 carbon atoms. Specific examples of L ² and L ³ include the groups described as the divalent hydrocarbon group described in the specification of the present case.

In L ² and L ³ , -CH = constituting the divalent hydrocarbon group may be substituted by -N =, and -CH ₂ -constituting the divalent hydrocarbon group may be substituted by an oxygen atom, a sulfur atom, and -N (R ⁵⁵ ) -, A sulfofluorenyl group or a carbonyl group, the hydrogen atom contained in the divalent hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, an aminesulfonyl group, -SO ₃ M ³ , -CO ₂ M ³ , hydroxyl, formamyl or amine.

Examples of L ² and L ³ include groups represented by the formulas (L23-1) to (L23-22). ● indicates a key-bond key.

[Chemical 12]

As L ² , the bases represented by the formulae (L23-1) to (L23-4) are preferred, the bases represented by the formulae (L23-1) and (L23-2) are more preferred, and the formulas are particularly preferred. (L23-2). If L ^{2 is} such a group, it is easy to synthesize.

As L ³ , a base represented by formula (L23-1), formula (L23-2), and formula (L23-5) to formula (L23-20) is more preferred, and formula (L23-1) and formula are more preferred (L23-2), formula (L23-5), formula (L23-7) to formula (L23-10), formula (L23-13) to formula (L23-20). If L ^{3 is} such a group, it is easy to synthesize.

R ³ represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a group represented by formula (z).

Examples of the base represented by the formula (z) include the following.

In formula (z), L ²² and L ³³ each independently represent a divalent hydrocarbon group having 1 to 30 carbon atoms.

L ²² and L ³³ have the same meanings as L ² and L ³ described above, respectively.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms of R ³ include one or more types of hydrocarbon groups selected from the group consisting of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups exemplified in R ¹ and R ² .

In R ³ , a hydrogen atom contained in the monovalent hydrocarbon group may be substituted with a halogen atom, a hydroxyl group, or a carboxyl group, and -CH ₂ -constituting the monovalent hydrocarbon group may be substituted with a carbonyl group. When a plurality of R ³ are present, they may be the same as or different from each other.

L ^{22 is} preferably a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably a straight or branched chain alkylene group having 1 to 8 carbon atoms, and still more preferably an ethyl or methyl ethyl group.

L ^{33 is} preferably a divalent aliphatic hydrocarbon group or an aromatic hydrocarbon group which may be substituted by a carboxyl group or a halogen atom, and more preferably a straight or branched chain alkyl group or an alkyl group having 1 to 8 carbon atoms which may be substituted by a carboxyl group or a halogen atom The phenyl group is more preferably an ethylidene group or a phenylene group which may be substituted with a carboxyl group or a halogen atom.

L ^{2 is} preferably a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably a straight or branched chain alkylene group having 1 to 8 carbon atoms, and still more preferably ethyl or methyl ethyl.

L ^{3 is} preferably a divalent aliphatic hydrocarbon group or an aromatic hydrocarbon group which may be substituted by a carboxyl group or a halogen atom, and more preferably a straight or branched chain alkyl group or an alkyl group having 1 to 8 carbon atoms which may be substituted by a carboxyl group or a halogen atom. The phenyl group is more preferably an ethylidene group or a phenylene group which may be substituted with a carboxyl group or a halogen atom.

In L ²² and L ³³ , -CH = constituting the divalent hydrocarbon group may be substituted by -N =, and -CH ₂ -constituting the divalent hydrocarbon group may be substituted by an oxygen atom, a sulfur atom, and -N (R ⁴⁴ ) -, A sulfofluorenyl group or a carbonyl group, the hydrogen atom contained in the divalent hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, an sulfamoyl group, -SO ₃ M ³ , -CO ₂ M ³ , hydroxyl, formamyl or amine.

M ¹ represents a hydrogen atom or an alkali metal atom. When a plurality of M ¹ exist, they may be the same as or different from each other.

R ³³ represents a hydrogen atom or -L ²² -OCO-L ³³ -CO ₂ M ² .

R ⁴⁴ and R ^{55 each} represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ⁴⁴ and R ⁵⁵ are present, they may be the same or different from each other. R ⁴⁴ and R ⁵⁵ may be at least one hydrocarbon group selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group exemplified in the above-mentioned R ¹ and R ² .

M, M ² and M ³ represent a hydrogen atom or an alkali metal atom, preferably a hydrogen atom, a sodium atom or a potassium atom, and more preferably a hydrogen atom. When there are a plurality of these cases, they may be the same as or different from each other.

Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.

Specific examples of the compound represented by the formula (I) and the compound represented by the formula (II) are shown in Tables 1 to 4. In Tables 1 to 8, "Et" represents an ethyl group, "Oct" represents an n-octyl group, and L1-1 to L1-43 respectively represent the formulas (L1-1) to (L1-43) illustrated above. The base.

From the viewpoint of easy synthesis, the formulae (I-9) to (I-19), (I-25) to (I-43), and (I-52) to (I- 62), formula (I-68) to formula (I-86), formula (I-95) to formula (I-105), formula (I-111) to formula (I-129), formula (I-138 ) ~ Formula (I-148) and Formula (I-154) ~ Compounds represented by Formula (I-172), more preferably Formula (I-9) ~ Formula (I-12), Formula (I-14) Formula (I-17) to Formula (I-19), Formula (I-25) to Formula (I-43), Formula (I-52) to Formula (I-55), Formula (I-57), Formula (I-60) to Formula (I-62), Formula (I-68) to Formula (I-86), Formula (I-95) to Formula (I-98), Formula (I-100), Formula (I-103) ~ Formula (I-105), Formula (I-111) ~ Formula (I-129), Formula (I-138) ~ Formula (I-141), Formula (I-143), Formula ( I-146) ~ Formula (I-148) and Formula (I-154) ~ Compounds represented by Formula (I-172), particularly preferably Formula (I-10), Formula (I-33), Formula (I -34), a compound represented by Formula (I-96), Formula (I-117), Formula (I-118), Formula (I-119), Formula (I-120).

As a method for producing the compound (I), a compound represented by the formula (pa1) and chlorosulfonic acid can be reacted to produce a compound represented by the formula (pa2), and then, the formula (pa2) can be produced. The compound represented by) and the compound represented by formula (pa3) are reacted in the presence of a solvent.

The reaction temperature of the compound represented by formula (pa1) and chlorosulfonic acid is preferably 0 ° C to 200 ° C, more preferably 30 ° C to 150 ° C, and more preferably 50 ° C to 150 ° C.

The reaction temperature of the compound represented by the formula (pa2) and the compound represented by the formula (pa3) is preferably -100 ° C to 100 ° C, more preferably -78 ° C to 80 ° C, and further preferably 0 ° C to 60 ° C. ℃.

Examples of the solvent used in the reaction between the compound represented by formula (pa2) and the compound represented by formula (pa3) include methanol, ethanol, isopropanol, acetonitrile, tetrahydrofuran, acetone, and 3-methyl-2-pentane. Ketone, ethyl acetate, hexane, toluene, methylene chloride, chloroform, N, N-dimethylformaldehyde and N-methylpyrrolidone, etc., preferably acetonitrile, N, N-dimethylformaldehyde and N -Methylpyrrolidone.

The compound represented by formula (pa2) and the compound represented by formula (pa3) may be reacted in the presence of a base or an alkali metal. The base is preferably a tertiary amine, a compound having a pyridine skeleton, and an organometallic compound. Specific examples include triethylamine, pyridine, 4-dimethylaminopyridine, methyllithium, and phenyl. Lithium, butyllithium, second butyllithium, and third butyllithium, and the like are preferably pyridine, 4-dimethylaminopyridine, and butyllithium. Examples of the alkali metal include sodium and lithium, and lithium is preferred.

[Chemical 14]

[In formulae (pa1), (pa2), and (pa3), R ¹ to R ² , X, n, L ^1, and M have the same meanings as described above.

In formula (pa3), XX represents a hydrogen atom, a halogen atom, * -O-toluenesulfonyl or * -O-methanesulfonyl. * Indicates a key-bond key]

In the production of the compound (pa2), the amount of chlorosulfonic acid used is usually 1 mol to 100 mol, preferably 5 mol to 60 mol, relative to 1 mol of the compound represented by formula (pa1). , More preferably 10 mol to 40 mol.

In the production of the compound (I), the amount of the compound represented by the formula (pa3) is usually 1 mole to 100 moles, preferably 1 mole relative to the compound represented by the formula (pa2). Ears ~ 80 moles, more preferably 1 ~ 60 moles.

The method for producing compound (II) can be produced by reacting a compound represented by formula (pa4) and a compound represented by formula (pa5) in the presence of a base and a solvent. The reaction temperature is preferably 0 ° C to 200 ° C, more preferably 0 ° C to 150 ° C, and even more preferably 50 ° C to 150 ° C.

The reaction time is preferably 1 hour to 36 hours, more preferably 2 hours to 30 hours, and even more preferably 3 hours to 28 hours.

As the base, a tertiary amine and a compound having a pyridine skeleton are preferred, and specifically In other words, triethylamine, pyridine, and 4-dimethylaminopyridine are mentioned, and pyridine and 4-dimethylaminopyridine are preferred.

Examples of the solvent include acetonitrile, tetrahydrofuran, acetone, 3-methyl-2-pentanone, ethyl acetate, hexane, toluene, dichloromethane, chloroform, N, N-dimethylformaldehyde, and N-formaldehyde. Pyrrolidone and the like are preferably N, N-dimethylformaldehyde and N-methylpyrrolidone.

[In formula (pa4) and formula (pa5), X, R ¹ to R ² , L ² to L ³ , R ³³ and n have the same meanings as described above]

In the production of the compound (II), the amount of the compound represented by the formula (pa5) is usually 1 mole to 200 moles, preferably 1 mole relative to the compound represented by the formula (pa4). Ears ~ 160 moles, more preferably 1 mole ~ 140 moles.

In the production of the compound (II), the amount of the tertiary amine and the compound having a pyridine skeleton is generally 0.1 mol to 80 mol, preferably 0.1 mol, relative to 1 mol of the compound represented by formula (pa4). Moore ~ 60 Moore, more preferably 0.1 ~ 45 Moore.

The production method of the formula (pa4) can be produced by reacting a compound represented by the formula (pa2) and a compound represented by the formula (pa6) in the presence of a solvent.

The reaction temperature of the compound represented by formula (pa2) and the compound represented by formula (pa6) is preferably 0 ° C to 100 ° C, more preferably 0 ° C to 80 ° C, and more preferably 0 ° C to 60 ° C.

Examples of the solvent used in the reaction between the compound represented by the formula (pa2) and the compound represented by the formula (pa6) include methanol, ethanol, isopropanol, acetonitrile, tetrahydrofuran, acetone, and 3-methyl-2-pentane. Ketone, ethyl acetate, hexane, toluene, methylene chloride, chloroform, N, N-dimethylformaldehyde and N-methylpyrrolidone, etc., preferably acetonitrile, N, N-dimethylformaldehyde and N -Methylpyrrolidone.

[In formula (pa6), R ³³ and L ^{2 have} the same meanings as described above]

In the production of the compound (pa4), the amount of the compound represented by the formula (pa6) is usually 1 mole to 100 moles, preferably 1 mole relative to the compound represented by the formula (pa2). Ears ~ 80 moles, more preferably 1 ~ 60 moles.

The compound represented by formula (pa2) is a Vilsmeier using N, N-dimethylformamide and thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, or ethylenedichloride in the presence of a solvent. The reaction is synthesized from a compound represented by formula (pa7).

[In formula (pa7), R ¹ to R ² , X and n have the same meanings as described above.

M 'represents a hydrogen atom, an alkali metal atom, or NH ₄ . In the case of a plurality of M ', they may be the same or different from each other]

The reaction temperature is preferably 0 ° C to 200 ° C, more preferably 0 ° C to 150 ° C, and even more preferably 0 ° C to 100 ° C.

The reaction time is preferably 1 hour to 72 hours, more preferably 1 hour to 48 hours, and even more preferably 1 hour to 24 hours.

Examples of the solvent include acetonitrile, tetrahydrofuran, acetone, 3-methyl-2-pentanone, ethyl acetate, hexane, toluene, dichloromethane, chloroform, and 1,4-dichloromethane. Alkane, N, N-dimethylformaldehyde and N-methylpyrrolidone, etc., preferably acetonitrile, 1,4-bis Alkane, N, N-dimethylformaldehyde and N-methylpyrrolidone.

In the production of the compound represented by formula (pa2), the amount of N, N-dimethylformamide used is usually 1 mole to 50 moles relative to 1 mole of the compound represented by formula (pa7). It is preferably 1 mol to 40 mol, and more preferably 1 mol to 30 mol.

In the production of the compound represented by formula (pa2), the amount of thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, or ethylenedichloride used is 1 mole relative to the compound represented by formula (pa7), It is usually 1 to 50 mol, preferably 1 to 40 mol, and more preferably 1 to 30 mol.

The method for obtaining the compound (I), compound (II), compound represented by formula (pa2), or compound represented by formula (pa4) of the present invention from the reaction mixture is not particularly limited, and various known methods can be adopted.

For example, a method may be mentioned in which the reaction mixture is added to a solvent in which the compound (I), the compound (II), the compound represented by the formula (pa2) or the compound represented by the formula (pa4) does not dissolve, and the method is used to crystallize. After precipitation, the crystals were removed by filtration; the reaction mixture was dissolved in tetrahydrofuran, acetone, acetic acid, ethyl acetate, hexane, toluene, chloroform or a mixed solution thereof, and then water, sodium hydroxide aqueous solution, acetic acid aqueous solution, hydrochloric acid, Sodium chloride water The solution, sodium bicarbonate aqueous solution or sodium carbonate aqueous solution is washed and then dried; or the solvent of the reaction mixture is distilled off, and then purified by column chromatography.

Further, purification can be performed by a known method such as column chromatography or recrystallization.

<Coloring agent of the present invention>

The coloring agent of the present invention (hereinafter sometimes referred to as "colorant (A)") contains, for example, compound (I) or compound (II) as an active ingredient. The colorant (A) may contain only the compound (I) or the compound (II), and may also contain a dye or pigment other than the compound (I) or the compound (II). The colorant (A) preferably contains a pigment in addition to the compound (I) or the compound (II). The content ratio of the compound (I) or the compound (II) in the colorant (A) is usually 1 to 100% by mass, preferably 3 to 100% by mass, more preferably 3 to 70% by mass, and further preferably 3 ~ 60% by mass.

The colorant (A) can be used as a coloring agent contained in a coloring resin composition used in a color filter of a display device such as a liquid crystal display device.

Examples of dyes other than compound (I) or compound (II) include: Solvent, Acid, and Basic classified in the Colour Index (published by The Society of Dyers and Colourists) ), Reactive, direct, disperse, or reduced compounds, or the well-known dyes described in Dyeing note. Examples of the chemical structure include azo dyes, anthraquinone dyes, triphenylmethane dyes, Dyes and phthalocyanine dyes. These dyes can be used alone or in combination of two or more.

Specifically, dyes with the following color index (C.I.) numbers can be listed. CI solvent yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI reaction yellow 2, 76, 116; CI direct yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141; CI Disperse Yellow 51 , 54, 76; CI solvent orange 2, 7, 11, 15, 26, 41, 54, 56, 99; CI acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62 , 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173; CI reaction orange 16; CI direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57 , 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; CI Acid Red 73, 80, 91, 92, 97, 138 , 151, 211, 274, 289; CI acid violet 34, 102; CI disperse violet 26, 27; CI solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI 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; CI Acid Blue 25, 27, 40, 45, 78, 80, 112; CI Direct Blue 40; CI Disperse Blue 1, 14, 56, 60; C.I. Solvent Green 1, 3, 5, 28, 29, 32, 33; C.I. Acid Green 3, 5, 9, 25, 27, 28, 41; C.I. Basic Green 1; C.I. Reduced Green 1 and the like.

The pigment is not particularly limited, and known pigments can be used, and examples thereof include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists). These pigments can be used alone or in combination of two or more.

Specifically, CI pigment yellow 1, 3, 12, 13, 14, 15, 16, 16, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; 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 and other red pigments; CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; CI Pigment Violet 1, 19, 23, 29 , 32, 36, 38 and other purple pigments; CI Pigment Green 7, 36, 58, 59 and other green pigments; CI Pigment Brown 23 and 25 and other brown pigments; and CI Pigment Black 1, 7 and other black pigments.

Among green pigments and blue pigments, phthalocyanine pigments are preferred, at least one selected from the group consisting of copper halide phthalocyanine pigments and zinc halide phthalocyanine pigments, and particularly preferably selected from CI Pigment Green 7 , 36, 58 and 59. These pigments are suitable for use as green colorants. By using a coloring agent containing these pigments, it is possible to form a color filter whose transmission spectrum is easily optimized and which has good light resistance or chemical resistance.

If necessary, the pigment can be subjected to rosin treatment, surface treatment using a pigment derivative introduced with an acidic group or a basic group, grafting treatment on the surface of the pigment with a polymer compound, or the like by a sulfuric acid micronization method. Micronization treatment, cleaning treatment for removing impurities using an organic solvent or water, etc., and removal treatment for ionic impurities using an ion exchange method or the like. The particle diameter of the pigment is preferably substantially uniform. By dispersing the pigment with a pigment dispersant, the pigment dispersion liquid can be prepared in a state where the pigment is uniformly dispersed in the pigment dispersant solution. The pigment may be separately dispersed, or a plurality of pigments may be mixed and then dispersed.

Examples of the pigment dispersant include a surfactant, and may be any of a cationic, anionic, nonionic, and amphoteric surfactant. Specific examples include surfactants such as polyester-based, polyamine-based, and acrylic-based surfactants. These pigment dispersants may be used alone or in combination of two or more. As a pigment dispersant, if it is represented by a trade name, KP (Shin-Etsu Chemical Industry Co., Ltd.), Flowlen (Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (Zeneca) , EFKA (registered trademark) (manufactured by BASF), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-Techno), Disperbyk (registered trademark) (manufactured by BYK-Chemie), and the like.

When a pigment dispersant is used, the amount used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the pigment. When the amount of the pigment dispersant used is in the above range, there is a tendency to obtain a pigment dispersion liquid with a more uniform dispersion state.

<Coloring resin composition of the present invention>

The colored resin composition of the present invention includes a colorant (A), a resin (hereinafter sometimes referred to as "resin (B)"), a polymerizable compound (hereinafter sometimes referred to as "polymerizable compound (C)"), and a polymerization agent. Initiator (hereinafter sometimes referred to as "polymerization initiator (D)") and solvent (hereinafter sometimes referred to as "solvent (E)"). The colored resin composition of the present invention may contain a leveling agent in addition to these components. The colored resin composition of the present invention may contain a polymerization initiation aid in addition to these components. Agent. In another aspect of the present invention, the colored resin composition may include a colorant (A), a resin (B), a solvent (E), and a surfactant as needed.

The content of the coloring agent (A) in the colored resin composition is usually 1% by mass or more and 70% by mass or less, preferably 1% by mass or more and 60% by mass or less with respect to the total amount of the solid components. It is more preferably 5 mass% or more and 60 mass% or less, and even more preferably 5 mass% or more and 50 mass% or less. When the content rate of the colorant (A) is within the above range, it is easier to obtain a desired spectroscopic or color density. The "total amount of solid components" in this specification refers to the total amount of components remaining after the solvent is removed from the colored resin composition of the present invention. The total amount of solid components and the content of each component relative thereto can be measured, for example, by known analysis methods such as liquid chromatography and gas chromatography.

<Resin (B)>

The resin (B) contained in the colored resin composition of the present invention is preferably an alkali-soluble resin, and more preferably has a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. Addition polymer. Examples of such resins include the following resins [K1] to [K6].

Resin [K1]: at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (a) (hereinafter sometimes referred to as "(a)"), and a ring having 2 to 4 carbon atoms Copolymer of an ether structure and an ethylenically unsaturated bond monomer (b) (hereinafter sometimes referred to as "(b)")

Resin [K2]: (a), (b), and monomer (c) (other than (a) and (b)) capable of copolymerizing with (a) (hereinafter sometimes referred to as "(c) '') Copolymer

Resin [K3]: copolymer of (a) and (c)

Resin [K4]: A resin obtained by reacting a copolymer of (a) with (c) and (b)

Resin [K5]: A resin obtained by reacting a copolymer of (b) with (c) and (a)

Resin [K6]: A resin obtained by reacting a copolymer of (b) with (c) and (a), and further reacting with a carboxylic anhydride.

Examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, butenoic acid, ortho / m / p-vinylbenzoic acid; maleic acid, fumaric acid, citraconic acid, Zhongconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrobenzene Unsaturated dicarboxylic acids such as formic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5-decane Ene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] -2-heptene, 5,6-dicarboxybicyclo [2.2.1] -2-heptene, 5-carboxy-5 -Methylbicyclo [2.2.1] -2-heptene, 5-carboxy-5-ethylbicyclo [2.2.1] -2-heptene, 5-carboxy-6-methylbicyclo [2.2. 1] -2-heptene, 5-carboxy-6-ethylbicyclo [2.2.1] -2-heptene unsaturated compounds containing carboxyl groups; maleic anhydride, citraconic anhydride, Ikon Acid anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, Unsaturated dicarboxylic anhydrides such as dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] -2-heptene anhydrous; succinate mono [2- (meth) acrylic acid Unsaturated mono [(meth) acryloxyalkyl] esters of polybasic polycarboxylic acids, such as ethyl ethyl] ester, mono [2- (meth) acryloxyethyl] phthalate ; Α- (hydroxymethyl) acrylate is equal to unsaturated acrylate containing hydroxyl and carboxyl groups in the same molecule.

Among these, acrylic acid, methacrylic acid, and maleic anhydride are preferable from the viewpoints of copolymerization reactivity or solubility of the obtained resin in an alkaline aqueous solution.

(b) A polymerizable compound having a cyclic ether structure (for example, an ethylene oxide ring, an oxetane ring, a tetrahydrofuran ring, etc.) having 2 to 4 carbon atoms and an ethylenically unsaturated bond. (b) A monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acrylic fluorenyloxy group is preferred. In addition, in this specification, "(meth) acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid, "(meth) acrylfluorenyl", and "(meth) acrylic acid" The expression "ester" has the same meaning.

Examples of (b) include a monomer (b1) having an ethylene oxide group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), an oxetanyl group and an ethylenic unsaturated group. A monomer (b2) (hereinafter sometimes referred to as "(b2)") and a monomer (b3) (hereinafter sometimes referred to as "(b3)") having a tetrahydrofuranyl group and an ethylenically unsaturated bond.

Examples of (b1) include a monomer (b1-1) having a structure obtained by epoxidizing a linear or branched aliphatic unsaturated hydrocarbon (hereinafter sometimes referred to as "(b1-1)" ), And a monomer (b1-2) (hereinafter sometimes referred to as "(b1-2)") having a structure obtained by epoxidation of an alicyclic unsaturated hydrocarbon.

As (b1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferred. Specific examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, and glycidyl Glyceryl vinyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl -M-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxy) (Meth) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxy) (Meth) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris ( Glycidyloxymethyl) styrene and 2,4,6-tris (glycidyloxymethyl) styrene.

Examples of (b1-2) include vinyl cyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000; manufactured by Daicel), and (a Base) 3,4-epoxycyclohexyl methyl acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel); 3,4-epoxy cyclohexyl methyl (meth) acrylate (for example, Cyclomer M100; Daicel (Product), a compound represented by formula (1), and a compound represented by formula (2).

[Chemical 18]

(In the formula, R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. X ^a and X ^b each independently represent a single bond, * ^{-R c -, * - R c} -O -, * - R c -S- or * -R ^c -NH-.R ^c alkanediyl group having a carbon number of 1 to 6, and * indicates the bond O bond. )

Examples of the alkyl group having 1 to 4 carbon atoms of R ^a and R ^b include methyl, ethyl, propyl, isopropyl, butyl, second butyl, and third butyl. Examples of the alkyl group in which a hydrogen atom of R ^a and R ^b is substituted with a hydroxy group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3- Hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, and 4-hydroxybutyl.

R ^a and R ^b are each independently preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and specifically, Is preferably a hydrogen atom, a methyl group, an ethyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

Examples of the alkanediyl group having 1 to 6 carbon atoms of R ^c include straight-chain or branched alkanediyl groups. Specific examples include methylene, ethylidene, and propane-1,3-diyl. Linear, butane-1,4-diyl, pentane-1,5-diyl, and hexane-1,6-diyl, linear alkanediyl; branched chains such as propane-1,2-diyl Like alkanediyl.

X ^a and X ^b are each independently preferably a single bond, * - R ^c - or * -R ^c -O-, more preferably a single bond or * -R ^c -O-, specifically, is preferably a single bond , Methylene, ethylene, * -CH ₂ -O- or * -CH ₂ CH ₂ -O-, more preferably a single bond or * -CH ₂ CH ₂ -O-. In the above formula, * represents a bond with O.

Examples of the compound represented by formula (1) include compounds represented by formula (1-1) to formula (1-15). Of these compounds, formulas (1-1), (1-3), (1-5), (1-7), (1-9), and (1-11) ~ The compound represented by Formula (1-15) is more preferably a compound represented by Formula (1-1), Formula (1-7), Formula (1-9), and Formula (1-15).

[Chemical 23]

Examples of the compound represented by the formula (2) include compounds represented by the formulae (2-1) to (2-15). Among them, the formulae (2-1), (2-3), and (2) are preferred. The compounds represented by (2-5), formula (2-7), formula (2-9), and formula (2-11) to formula (2-15), more preferably formula (2-1), formula ( 2-7), compounds represented by formula (2-9) and formula (2-15).

[Chemical 27]

[Chemical 32]

The compound represented by the formula (1) and the compound represented by the formula (2) may be used alone, or the compound represented by the formula (1) and the compound represented by the formula (2) may be used in combination. When these are used in combination, the ratio of the compound represented by formula (1) to the compound represented by formula (2) (compound represented by formula (1): compound represented by formula (2)) is on a Mohr basis It is preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and still more preferably 20:80 to 80:20.

As (b2), a monomer having an oxetanyl group and a (meth) acryloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, 3- Ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-propenemethyloxetane, 3-methyl-3-methacryloxy Ethylethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3- Ethyl-3-methacryloxyethyloxetane and 3-ethyl-3-propenyloxyethyloxetane.

As (b3), a monomer having a tetrahydrofuranyl group and a (meth) acryloxy group is more preferable. Examples of (b3) include tetrahydrofuran methyl acrylate (for example, Viscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofuran methyl methacrylate.

In terms of being able to further improve the reliability such as heat resistance and chemical resistance of the obtained color filter, (b) is preferably (b1), and in terms of excellent storage stability of the colored resin composition, In other words, (b1) is preferably (b1-2).

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, and third (meth) acrylate Butyl, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate Ester, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, {tricyclo [5.2.1.0 ^2,6 ] decane-8-yl} (meth) acrylate (in In this technical field, a common name is called "dicyclopentyl (meth) acrylate." It is also sometimes called "tricyclodecyl (meth) acrylate.") Cyclic [5.2.1.0 ^2,6 ] decene-8-yl} ester (in this technical field, it is commonly called "dicyclopentenyl (meth) acrylate"), (meth) acrylic acid Dicyclopentyloxyethyl, (meth) acrylic iso Ester, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, (meth) ) (Meth) acrylates such as benzyl acrylate; hydroxyl-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; maleic acid di Dicarboxylic acid diesters such as ethyl ester, diethyl fumarate, diethyl itaconic acid, etc .; bicyclo [2.2.1] -2-heptene, 5-methylbicyclo [2.2.1]- 2-heptene, 5-ethylbicyclo [2.2.1] -2-heptene, 5-hydroxybicyclo [2.2.1] -2-heptene, 5-hydroxymethylbicyclo [2.2.1] -2-heptene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] -2-heptene, 5-methoxybicyclo [2.2.1] -2-heptene, 5-ethyl Oxybicyclo [2.2.1] -2-heptene, 5,6-dihydroxybicyclo [2.2.1] -2-heptene, 5,6-bis (hydroxymethyl) bicyclo [2.2.1 ] -2-heptene, 5,6-bis (2'-hydroxyethyl) bicyclo [2.2.1] -2-heptene, 5,6-dimethoxybicyclo [2.2.1] -2 -Heptene, 5,6-diethoxybicyclo [2.2.1] -2-heptene, 5-hydroxy-5-methylbicyclo [2.2.1] -2-heptene, 5-hydroxy- 5-ethylbicyclo [2.2.1] -2-heptene, 5-hydroxymethyl-5-methyl Bicyclo [2.2.1] -2-heptene, 5-tert-butoxycarbonyl bicyclo [2.2.1] -2-heptene, 5-cyclohexyloxycarbonyl bicyclo [2.2.1] -2 -Heptene, 5-phenoxycarbonylbicyclo [2.2.1] -2-heptene, 5,6-bis (third butoxycarbonyl) bicyclo [2.2.1] -2-heptene, 5 , 6-Bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] -2-heptene and other bicyclic unsaturated compounds; N-phenylcis-butenedifluorene imine, N-cyclohexylcis-butenedi Fluorenimine, N-benzyl cis butene difluorenimide, N- succinimide imino-3-cis butylene fluorenimide benzoate, N- succinimide imino-4- Maleimide diimide butyrate, N-butamediolimide-6-maleimide diimide hexanoate, N-butadiimide imido-3-maleimide Dicarbonyl sulfonium imine compounds such as amino propionates, N- (9-acridyl) cis butene difluorene imine; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene , Vinyl toluene, p-methoxystyrene and other vinyl-containing aromatic compounds; vinyl nitriles such as acrylonitrile and methacrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; acrylamide, methyl Acetylamine, such as acrylamide; ethyl Vinyl esters like esters; 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like hexadiene.

Among these, from the viewpoints of copolymerization reactivity and heat resistance, a vinyl-containing aromatic compound, a dicarbonylamidine compound, and a bicyclic unsaturated compound are preferred. Specifically, styrene, vinyltoluene, benzyl (meth) acrylate, {tricyclo [5.2.1.0 ^2,6 ] decane-8-yl} ester of (meth) acrylic acid, and N-benzene are preferred. Cis-butene difluorene imine, N-cyclohexyl cis butene difluorene imine, N-benzyl cis butene difluorene imine and bicyclo [2.2.1] -2-heptene.

In the resin [K1], the ratio of the structural units derived from each of the resins, among all the structural units constituting the resin [K1], The structural unit derived from (a): 2 ~ 60 mole% The structural unit derived from (b): 40 ~ 98 mole%, more preferably the structural unit derived from (a): 10 ~ 50 mole Ear% is derived from the structural unit of (b): 50 ~ 90 mole%.

When the ratio of the structural unit of the resin [K1] is in the above range, there is a tendency that the storage stability of the colored resin composition, the developability when a colored pattern is formed, and the solvent resistance of the obtained color filter are more excellent.

The resin [K1] can be, for example, the method described in the document "Experimental Method of Polymer Synthesis" (by Otsu Takayuki, Issuing Agency: Chemical Associates, Ltd., 1st Edition, 1st Printing, March 1, 1972) and The references cited in this document are manufactured as a reference.

Specifically, the following methods can be enumerated: a specific amount of (a) and (b), a polymerization initiator, a solvent, and the like are charged into a reaction vessel, and for example, nitrogen is substituted for oxygen to form a deoxidizing environment, while stirring, while Heating and holding. The polymerization initiator, solvent, and the like used herein are not particularly limited, and those generally used in this field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) or organic peroxides. As the solvent, any solvent may be used as long as it dissolves each monomer, and examples of the solvent of the colored resin composition of the present invention described below are mentioned.

As for the obtained copolymer, a solution after the reaction may be used directly, a solution after concentration or dilution may be used, or a solid (powder) form extracted by a method such as reprecipitation may be used. In particular, since the solvent contained in the colored resin composition of the present invention is used as a solvent during the polymerization, the solution after the reaction can be directly used to prepare the colored resin composition of the present invention, so that the colored resin composition of the present invention can be simplified. Manufacturing steps.

In the resin [K2], the ratio of the structural units derived from each of the resins [K2] Among all the structural units, the structural unit derived from (a): 2 ~ 45 mole% Structural unit derived from (b): 2 ~ 95 mole% Structural unit derived from (c): 1 ~ 65 mol%, more preferably structural unit derived from (a): 5 ~ 40 mol% structural unit derived from (b): 5 ~ 80 mol% structural unit derived from (c): 5 ~ 60 Mohr%.

When the ratio of the structural unit of the resin [K2] is in the above range, there are storage stability of the colored resin composition, developability when a colored pattern is formed, and solvent resistance, heat resistance, and mechanical properties of the obtained color filter The strength tends to be more excellent.

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

In the resin [K3], regarding the ratio of the structural units derived from each, among all the structural units constituting the resin [K3], the structural unit derived from (a) is preferred: 2 to 60 mol% derived from ( c) structural unit: 40 ~ 98 mole%, more preferably the structural unit derived from (a): 10 ~ 50 mole% structural unit derived from (c): 50 ~ 90 mole%.

The resin [K3] can be produced, for example, in the same manner as described in the method for producing the resin [K1].

The resin [K4] can be obtained by copolymerizing (a) and (c) and adding a cyclic ether moiety having 2 to 4 carbon atoms in (b) to the carboxylic acid and / or (a) Or carboxylic anhydride. Specifically and In other words, it can be manufactured as follows. First, a copolymer of (a) and (c) is produced in the same manner as the method described as the production method of the resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same as the ratio listed for the resin [K3]. Then, a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer is reacted with a cyclic ether compound having 2 to 4 carbon atoms in (b). After the copolymers of (a) and (c) were produced, the gas in the flask was replaced by nitrogen with air, and the catalyst in the reaction between (b), the carboxylic acid or carboxylic anhydride and the cyclic ether compound ( For example, tris (dimethylaminomethyl) phenol, etc.) and polymerization inhibitors (eg, hydroquinone, etc.) are reacted at, for example, 60 to 130 ° C. for 1 to 10 hours, thereby producing a resin [K4].

Regarding the amount of (b) used, it is preferably 5 to 80 mol, and more preferably 10 to 75 mol relative to 100 a in (a). By adjusting the amount of (b) used in this range, the colored resin composition containing the obtained resin has storage stability, developability when forming a pattern, solvent resistance, heat resistance, and mechanical strength of the obtained pattern And the balance of sensitivity tends to be better. In terms of the high reactivity of the cyclic ether site and the unreacted (b) remaining less easily, (b) used for the resin [K4] is preferably (b1), more preferably (b1-1).

The used amount of the catalyst is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b), and (c). The usage-amount of the said polymerization inhibitor is 0.001-5 mass parts with respect to 100 mass parts of the total amount of (a), (b), and (c).

The reaction conditions such as the method of adding each reagent, the reaction temperature, and the reaction time can be appropriately adjusted in consideration of the amount of heat generated during production equipment or polymerization. In addition, the addition method and reaction temperature can be appropriately adjusted in consideration of the amount of heat generated during production equipment, polymerization, and the like, as in the polymerization conditions.

When producing the resin [K5], as the first step, the copolymers of (b) and (c) were obtained in the same manner as in the method for producing the resin [K1]. As for the obtained copolymer, as described above, a solution after the reaction may be used directly, a solution after concentration or dilution may be used, or a solid (powder) form extracted by a method such as reprecipitation may be used. In the first phase, about The ratio of the structural units derived from (b) and (c) is preferably derived from (b) with respect to the total mole number of all the structural units constituting the copolymer of (b) and (c) above. Structural unit: 5 ~ 95 mol% derived from (c) Structural unit: 5 ~ 95 mol%, more preferably derived from (b): 10 ~ 90 mol% derived from (c) Structural unit: 10 ~ 90 mol%.

Furthermore, as the second stage, under the same conditions as in the method for producing the resin [K4], the copolymer of (b) and (c) has the cyclic ether moiety derived from (b) and (a) A resin [K5] can be obtained by reacting a carboxylic acid or a carboxylic anhydride.

In the second stage, the amount of (a) to be reacted with the copolymer of (b) and (c) is preferably 5 to 80 moles relative to 100 moles of (b). In terms of the high reactivity of the cyclic ether site, and the unreacted (b) being less likely to remain, (b) used for the resin [K5] is preferably (b1), more preferably (b1-1).

The resin [K6] is a resin obtained by reacting the resin [K5] and further with a carboxylic acid anhydride, and specifically, by making the cyclic ether moiety derived from (b) and the carboxylic acid or carboxylic acid from (a) It is produced by reacting a hydroxyl group produced by an acid anhydride reaction with a carboxylic acid anhydride.

Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrobenzene Dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] -2-heptene anhydrous. The amount of carboxylic anhydride used is preferably 0.5 to 1 mole relative to the amount of (a) used.

Examples of the resin (B) include 3,4-epoxycyclohexyl methyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxy tricyclic (meth) acrylic acid [5.2.1.0 ^2,6 ] resins such as decyl ester / (meth) acrylic copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, (meth) acrylic acid Glycidyl ester / styrene / (meth) acrylic acid copolymer, (meth) acrylic 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl ester / (meth) acrylic acid / N-cyclohexyl cis Butene difluorene imine copolymer, 3,4-epoxytricyclic (meth) acrylic acid [5.2.1.0 ^2,6 ] decyl / (meth) acrylic acid / vinyl toluene copolymer, 3-methyl- 3- (meth) acryloxymethyloxetane / (meth) acrylic acid / styrene copolymer and other resins [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymer, Resins such as styrene / (meth) acrylic acid copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer [K3]; glycidyl (meth) acrylate Ester added to benzyl (meth) acrylate / (meth) acrylic acid copolymer resin, A resin obtained by adding glycidyl ester to tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, and adding glycidyl (meth) acrylate to tricyclic (meth) acrylate Decyl ester / benzyl (meth) acrylate / (meth) acrylic acid copolymer [K4]; Tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate copolymer Resin obtained by reacting with (meth) acrylic acid, resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate with (meth) acrylic acid And other resins [K5]; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid and further reacting with tetrahydrophthalic anhydride The obtained resin [K6].

The resin (B) is preferably selected from the group consisting of the resin [K1], the resin [K2], and the resin [K3], and more preferably selected from the group consisting of the resin [K1] and the resin [K2] One kind. With these resins, the colored resin composition is excellent in developability. From the viewpoint of adhesion between the colored pattern and the substrate, the resin [K1] is more preferable.

The polystyrene equivalent weight average molecular weight of the resin (B) is usually 3,000 to 100,000, preferably 5,000 to 50,000, more preferably 5,000 to 35,000, still more preferably 5,000 to 30,000, and even more preferably 6,000 to 30,000. When the molecular weight is in the above range, there is a tendency that the hardness of the coating film is increased, the residual film ratio is also 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 1.1 to 6, more preferably 1.2 to 4, and even more preferably 1.3 to 3.

The acid value of the resin (B) is preferably 20 to 170 mg-KOH / g, more preferably 30 to 170 mg-KOH / g, of which 40 to 170 mg-KOH / g is preferred, and 50 to 170 mg is preferred -KOH / g, more preferably 150 mg-KOH / g or less, and still more preferably 135 mg-KOH / g or less.

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 obtained by, for example, titration using an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65% by mass relative to the total amount of the solid components, of which 10 to 60% by mass is preferred, and 13 to 60% by mass is preferred, of which, It is preferably 17 to 55 mass%. When content of resin (B) exists in the said range, there exists a tendency for the resolution of a coloring pattern, a resolution of a coloring pattern, and a residual film rate to improve easily.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound capable of polymerizing under the action of an active radical and / or an acid generated by a polymerization initiator, and examples thereof include polymerizable compounds having an ethylenically unsaturated bond, and preferably having ( Compounds of meth) acrylate structure. The polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds, and more preferably a polymerizable compound having 5 to 6 ethylenically unsaturated bonds.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethylhexylcarbitol acrylate , 2-hydroxyethyl acrylate, N-vinyl pyrrolidone, (a), (b), and (c) above. Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, and neopentyl glycol di (methyl) Acrylate), triethylene glycol di (meth) acrylate, bis (acryloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate. Examples of the polymerizable compound having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Second season Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate Tetrapentaerythritol nine (meth) acrylate, tris (2- (meth) acryloxyethyl) 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, and hexane Lactone modified dipentaerythritol hexa (meth) acrylate.

Among these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferred.

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

The content of the polymerizable compound (C) in the colored resin composition of the present invention is usually 5 to 65% by mass, preferably 7 to 65% by mass, and more preferably 10 to 65% by mass relative to the total amount of solid components. 60 mass%, more preferably 13 to 60 mass%, and even more preferably 17 to 55 mass%. The content ratio of the resin (B) to the polymerizable compound (C) (resin (B): polymerizable compound (C)) is usually 20:80 to 80:20 on a mass basis, and preferably 35:65 ~ 80: 20. When the content of the polymerizable compound (C) is within the above range, there is a tendency that the residual film rate at the time of forming a colored pattern and the chemical resistance of the color filter are improved.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating active radicals, acids, etc. under the action of light or heat, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include an O-fluorenyl oxime compound, an alkyl phenone compound, and Compounds, fluorenyl phosphine oxide compounds, and biimidazole compounds.

The O-fluorenyl oxime compound is a compound having a structure represented by formula (d1). the following,* Represents a bond key.

Examples of the O-fluorenyl oxime compound include N-benzyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine and N-benzyloxy -1- (4-phenylthiophenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylthiophenyl) -3-cyclopentane Propane-1-one-2-imine, N-ethoxyl-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] ethyl Alkane-1-imine, N-ethoxyl-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxolane Methylmethyloxy) benzamidine} -9H-carbazol-3-yl] ethane-1-imine, N-ethoxymethyl-1- [9-ethyl-6- (2-methyl Benzamyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine and N-benzyloxy-1- [9-ethyl-6- (2- Methylbenzyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one-2-imine. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (the above are manufactured by BASF), and N-1919 (made by ADEKA) can also be used. Among them, it is preferably selected from the group consisting of N-benzyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine, N-benzyloxy-1- ( 4-phenylthiophenyl) octane-1-one-2-imine and N-benzyloxy-1- (4-phenylthiophenyl) -3-cyclopentylpropane-1 At least one of the group consisting of -keto-2-imine, more preferably N-benzyloxy-1- (4-phenylthiophenyl) octan-1-one-2-imine amine.

The alkyl phenone compound is a compound having a structure represented by formula (d2) or a structure represented by formula (d3). Furthermore, the benzene ring in these structures may have a substituent.

[Chemical 36]

Examples of the compound having a structure represented by the formula (d2) include 2-methyl-2-morpholinyl-1- (4-methylthiophenyl) propane-1-one and 2-dimethyl Amino-1- (4-morpholinylphenyl) -2-benzylbutane-1-one and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one. Commercial products such as Irgacure 369, 907, and 379 (the above are manufactured by BASF) can also be used.

Examples of the compound having a structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one and 2-hydroxy-2-methyl-1- [4- ( 2-hydroxyethoxy) phenyl] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one Oligomers, α, α-diethoxyacetophenone and benzophenone dimethyl ketal.

In terms of sensitivity, the alkyl phenone compound is preferably a compound having a structure represented by formula (d2).

As three Compounds include: 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-tri , 2,4-bis (trichloromethyl) -6-sunfloweryl-1,3,5-tri , 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3,5-tris And 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-tris .

Examples of the fluorenylphosphine oxide compound include 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide.

Examples of the biimidazole compound include compounds represented by formula (d4).

(In the formula, R ⁵¹ to R ⁵⁶ represent an aryl group having 6 to 10 carbon atoms which may have a substituent.)

Examples of the aryl group having 6 to 10 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, and naphthyl, and phenyl is preferred. Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferred. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a methoxy group is preferable.

Specific 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, refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2 , 2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5, 5'-tetrakis (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Japanese Patent Application Laid-Open No. 62-174204, etc.) and imidazole compounds substituted with phenylhydroxyalkoxycarbonyl at the 4,4 ', 5,5'-position (for example, refer to Japanese Patent Application Laid-Open No. 07-010913). Among them, a compound represented by the following formula and a mixture thereof are preferred.

[Chemical 38]

Examples of other polymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoyl benzoate, 4-benzene Benzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetrakis (third butylperoxycarbonyl) benzophenone, 2, 4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinone compounds; 10-butyl-2-chloroacridone, Benzozone, methyl phenylglyoxylate, titanocene compounds, etc. These are preferably used in combination with a polymerization initiation aid described later (especially, an amine-based polymerization initiation aid).

Examples of the acid-generating polymerization initiator include 4-hydroxyphenyldimethylfluorene p-toluenesulfonic acid, 4-hydroxyphenyldimethylfluorene hexafluoroantimonate, and 4-ethylphosphonium p-toluenesulfonic acid. Phenylphenyldimethylfluorene, hexafluoroantimonate 4-ethoxyphenylmethylbenzylfluorene, triphenylphosphonium p-toluenesulfonate, triphenylphosphonium hexafluoroantimonate, diphenylp-toluenesulfonic acid Onium salts such as hydrazone, diphenylphosphonium hexafluoroantimonate, nitrobenzyl tosylate, benzoin tosylate, and the like.

The polymerization initiator (D) is preferably a polymerization initiator that generates living radicals, and more preferably contains a polymer selected from the group consisting of At least one of the group consisting of a compound, a fluorenylphosphine oxide compound, an O-fluorenyl oxime compound, and a biimidazole compound, and further preferably an O-fluorenyl oxime compound.

The content of the polymerization initiator (D) is usually 0.1 to 40 parts by mass, preferably 0.1 to 30 parts by mass, and more preferably 100 parts by mass relative to the total amount of the resin (B) and the polymerizable compound (C). It is 1 to 30 parts by mass, and particularly preferably 1 to 20 parts by mass.

<Polymerization Initiation Auxiliary>

Polymerization initiation aid is used to promote the initiation of polymerization by the polymerization initiator (D). Polymerized compound or sensitizer of the polymerizable compound (C). When the colored resin composition of the present invention contains a polymerization initiator, it is usually used in combination with a polymerization initiator (D).

Examples of the polymerization initiation aid include amine-based polymerization initiation aid, alkoxyanthracene-based polymerization initiation aid, and 9-oxosulfur. Based polymerization initiation aid and carboxylic acid based polymerization initiation aid.

Examples of the amine-based polymerization initiator include alkanolamines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzene Ethyl benzoic acid such as ethyl formate, 4-dimethylamino isobenzoate, 2-dimethylamino ethyl benzoate, 2-ethylhexyl 4-dimethylamino benzoate Ester; N, N-dimethyl-p-toluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michelin), 4,4'-bis (diethylamino ) Benzophenone and 4,4'-bis (ethylmethylamino) benzophenone, among them, alkyl groups such as 4,4'-bis (diethylamino) benzophenone are preferred Aminobenzophenone. Among them, an alkylaminobenzophenone is preferred, and 4,4'-bis (diethylamino) benzophenone is more preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

Examples of the alkoxyanthracene-based polymerization initiator include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

As 9-oxysulfur Polymerization initiation aids, including: 2-isopropyl-9-oxysulfur 4-isopropyl-9-oxysulfur , 2,4-diethyl-9-oxysulfur , 2,4-dichloro 9-oxysulfur And 1-chloro-4-propoxy-9-oxysulfur .

Examples of the carboxylic acid-based polymerization initiator include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, and dimethylphenyl. Thioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid , Naphthylthioacetic acid, N-naphthylglycine and naphthyloxyacetic acid.

In the case of using a polymerization initiation adjuvant, its content is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C), and more preferably It is 1 to 20 parts by mass. When the content of the polymerization initiation aid is within this range, there is a tendency that a colored pattern can be formed at a higher sensitivity, and productivity of a color filter tends to be improved.

<Solvent (E)>

The solvent (E) is not limited, and solvents generally used in this field can be used alone or in a combination of two or more kinds. Specific examples include: ester solvents (solvents containing -COO- but not containing -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), and ether ester solvents (Solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (containing OH in the molecule, but -O-, -CO- and -COO- solvents), aromatic hydrocarbon solvents, amidine solvents and dimethyl sulfene.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, cyclohexane Alcohol 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, and Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, Tetrahydrofuran, tetrahydropyran, 1,4-di Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether and Methylanisole.

Examples of the ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid. Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethoxy Ethyl-2-methylpropanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol methyl ester Ether acetate.

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

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

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

Examples of the amidine solvents include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

These solvents may be used in combination of two or more.

Among the above solvents, an organic solvent having a boiling point of 120 ° C. or higher and 210 ° C. or lower at 1 atm in terms of coatability and drying properties is preferred. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and diethylene glycol are preferred. Monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-di Methylformamide and N-methylpyrrolidone, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, acetic acid 3-methoxybutyl ester, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, N, N-dimethylformamide and N-methylpyrrolidone.

The content of the solvent (E) is usually 70 to 95% by mass, preferably 75 to 92% by mass, and more preferably 75 to 90% by mass with respect to the total amount of the colored resin composition. When the content of the solvent (E) is in the above-mentioned range, the flatness at the time of coating becomes good, and the color density is not insufficient when the color filter is formed. Therefore, the display characteristics tend to be good.

<Leveling agent>

Examples of the leveling agent include a polysiloxane-based surfactant, a fluorine-based surfactant, and a polysiloxane-based surfactant having a fluorine atom. These may have a polymerizable group in a side chain.

Examples of the polysiloxane-based surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Dow Corning Toray (stock)), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (made by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.).

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specific examples include: Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass) and E5844 (manufactured by Daikin Institute of Precision Chemistry)

Examples of the polysiloxane-based 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, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, and MEGAFAC F443 (manufactured by DIC Corporation).

The content of the leveling agent is usually 0.0005 mass% or more and 0.6 mass% or less, preferably 0.001 mass% or more and 0.5 mass% or less, and more preferably 0.001 mass% or more with respect to the total amount of the colored resin composition. 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, particularly preferably 0.005% by mass or more and 0.07% by mass or less. If the content of the leveling agent is within the above range, the flatness of the color filter can be optimized.

<Other ingredients>

The colored resin composition of the present invention may further include additives known in the technical field such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents, if necessary.

<Manufacturing method of colored resin composition>

The colored resin composition of the present invention can be prepared by, for example, coloring agent (A), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E), and leveling agent as needed. , A polymerization initiation aid and other ingredients are prepared by mixing. In addition to the colorant (A), a pigment or a dye may be further mixed. Regarding the pigment, it is preferred to use it in a state of a pigment dispersion by mixing part or all of the solvent (E) in advance and dispersing it using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. In this case, a part or all of the pigment dispersant and the resin (B) may be blended as necessary.

The compound (I) is preferably prepared by dissolving a part or all of the solvent (E) in advance to prepare a solution. Furthermore, it is preferable to filter the solution with a filter having a pore size of about 0.01 to 1 μm.

It is preferred to filter the colored resin composition after mixing with a filter having a pore size of about 0.01 to 10 μm.

<Manufacturing method of color filter>

Examples of the method for producing a colored pattern from the colored resin composition of the present invention include a photolithography method, an inkjet method, and a printing method. Among them, photolithography is preferred. Light lithography The method is as follows: a colored resin composition is coated on a substrate and dried to form a colored composition layer, and the colored composition layer is exposed through a photomask to develop it. In the photolithography method, since a photomask is not used during exposure and / or development is not performed, a colored coating film can be formed as a cured product of the coloring composition layer. The colored pattern or colored coating film thus formed is the color filter of the present invention.

The film thickness of the produced color filter can be appropriately adjusted according to the purpose or application, and is usually 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, soda-lime glass coated with silicon oxide, or polycarbonate, polymethyl methacrylate, and polyterephthalic acid can be used. Resin plates, such as ethylene glycol, and silicon, are formed on the substrate with aluminum, silver, silver / copper / palladium alloy films, or the like. Other color filter layers, resin layers, transistors, circuits, etc. can also be formed on these substrates.

The formation of the pixels of various colors by the photolithography method can be performed under known or customary devices or conditions. For example, it can be produced as follows.

First, a colored resin composition is coated on a substrate, followed by heating drying (pre-baking) and / or drying under reduced pressure to remove and dry volatile components such as solvents, thereby obtaining a smooth colored composition layer. Examples of the coating method include a spin coating method, a slit coating method, and a slit + spin coating method. In the case of heating and drying, the temperature is preferably 30 to 120 ° C, and more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. In the case of drying under reduced pressure, it is preferably performed under a pressure of 50 to 150 Pa and a temperature range of 20 to 25 ° C. The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected depending on the target film thickness of the color filter.

Then, the coloring composition layer is exposed through a mask for forming a target coloring pattern. The pattern on the mask is not particularly limited, and a pattern corresponding to the intended use can be used. As a light source used for the exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferred. It is also possible, for example, to use light filters that cut off the wavelength range for light up to 350 nm. Cut off, or use a band-pass filter that captures these wavelength regions to selectively capture light near 436nm, 408nm, and 365nm. Specific examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp. In order to be able to uniformly irradiate parallel light on the entire exposure surface, or accurately position the photomask and the substrate on which the coloring composition layer is formed, it is preferable to use an exposure device such as a photomask alignment exposure machine and a stepping exposure machine. . After the exposed coloring composition layer is brought into contact with a developing solution and developed, a coloring pattern is formed on the substrate. The unexposed portion of the coloring composition layer is dissolved in a developing solution by development to remove it. As the developing solution, an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide is preferred. The concentration of the basic compound is preferably 0.01 to 10% by mass, and more preferably 0.02 to 5% by mass. The developer may also contain a surfactant. The developing method may be any of a liquid coating method, a dipping method, and a spray method. Furthermore, the substrate can be tilted at an arbitrary angle during development. After development, washing with water is preferred.

It is preferable to further post-bake the obtained colored pattern. The post-baking temperature is preferably 150 to 250 ° C, and more preferably 160 to 235 ° C. The post-baking time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes. In order to impart various characteristics to the thus obtained color filter having a colored pattern or a colored coating film, it may be further subjected to a surface coating treatment.

The color filter formed from the colored resin composition of the present invention can be used as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements.

[Example]

Next, the present invention will be described more specifically with reference to examples. In the examples, "%" and "part" refer to mass% and mass parts unless otherwise specified.

In the following synthesis examples, the structure of the compound was analyzed by NMR (JMM-ECA-500; manufactured by JEOL Ltd.) or mass spectrometry (LC; Model 1200 manufactured by Agilent, MASS; Model LC / MSD6130 manufactured by Agilent) confirm.

Polystyrene equivalent weight average molecular weight (Mw) and number average molecular weight of resin The measurement of (Mn) was performed by the GPC method under the following conditions.

Device: HLC-8120GPC (manufactured by Tosoh)

Column: TSK-GELG2000HXL

Column temperature: 40 ℃

Solvent: THF

Flow rate: 1.0mL / min

Concentration of the solid content of the tested solution: 0.001 ~ 0.01% by mass

Injection volume: 50 μL

Detector: RI

Calibration Standards: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh)

The ratio of the weight-average molecular weight to the number-average molecular weight (Mw / Mn) in terms of polystyrene conversion obtained above was defined as the molecular weight distribution.

Example 1

25.3 parts of coumarin 6 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 206 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 120 ° C. for 4.5 hours. The mixture was cooled to 10 ° C and dropped into a mixture of 750 parts of ice and 750 parts of water. During the dropwise addition, the temperature of the mixture of ice and water to which the above mixture was dropped was maintained at 10 ° C. Suction filtration was performed to obtain insoluble matter as a residue. 1,000 parts of water at 10 ° C was added to the residue, and the mixture was stirred while maintaining the temperature of the mixture at 10 ° C, followed by suction filtration to obtain an insoluble matter as a residue. 196 residues were obtained. A mixture of 35.0 parts of DL-1-amino-2-propanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 502 parts of acetonitrile was added to 99.6 parts of the residue, and the mixture was stirred at room temperature for 3 hours. Thereafter, the mixture was stirred at 40 ° C for 1 hour. The mixture was cooled to room temperature, 2220 parts of chloroform and 1500 parts of a 2.5% sodium hydroxide aqueous solution were added and stirred, and then left to stand. The chloroform solution layer was extracted, and 1500 parts of a 10% acetic acid aqueous solution was added and stirred, and then left to stand. The chloroform solution layer was extracted, dried over magnesium sulfate, and then filtered. Benefits to the filtrate After distilling off the solvent with a rotary evaporator, it was dried under reduced pressure at 60 ° C to obtain 12.0 parts of a compound represented by formula (I-96).

<Identification of compound represented by formula (I-96)>

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 488

Exact Mass: 487

Example 2

1.03 parts of the compound represented by the formula (I-96) obtained above, 0.238 parts of succinic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.0370 Parts and 35.0 parts of 1-methyl-2-pyrrolidone (manufactured by Nacalai Tesque (stock)) were mixed and stirred at 70 ° C for 2.5 hours. To this mixture were added 1.07 parts of succinic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.287 parts of 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.), and the mixture was stirred at 70 ° C. for 18 hours. To this mixture, 300 parts of 1N hydrochloric acid and 444 parts of chloroform were added, stirred, and then left to stand. The chloroform solution layer was extracted, washed twice with 300 parts of 1N hydrochloric acid, and once with 300 parts of a 10% acetic acid aqueous solution. The chloroform solution layer was dried with magnesium sulfate, and then filtered. The solvent was distilled off from the filtrate by a rotary evaporator, and the obtained residue was added to 200 parts of water. To this mixture was added 444 parts of chloroform, followed by stirring, and then left to stand. The chloroform solution layer was extracted, dried over magnesium sulfate, and then filtered. The solvent was distilled off from the filtrate by a rotary evaporator, and then dried under reduced pressure at 60 ° C. dry. 5.00 parts of N, N-dimethylformamide was added to the obtained residue, and after stirring, it was dripped into 200 parts of 18% sodium chloride aqueous solution. To this mixture was added 444 parts of chloroform, followed by stirring, and then left to stand. The chloroform solution layer was extracted, dried over magnesium sulfate, and then filtered. The solvent was distilled off from the filtrate using a rotary evaporator. 5.06 parts of N, N-dimethylformamide was added to the obtained residue, and after stirring, it was dripped into 300 parts of 18% sodium chloride aqueous solution. Suction filtration was performed to obtain insoluble matter as a residue. This residue was dried under reduced pressure at 60 ° C to obtain 1.21 parts of a compound represented by formula (I-117).

<Compound represented by Formula (I-117)>

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 588

Accurate quality: 587

Example 3

1.07 parts of the compound represented by the formula (I-96) obtained above, 3.28 parts of phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) ) 0.556 parts and 37.0 parts of 1-methyl-2-pyrrolidone (manufactured by Nacalai Tesque (stock)) were mixed and stirred at 100 ° C. for 17.5 hours. To this mixture were added 1.68 parts of phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.277 parts of 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.), and the mixture was stirred at 100 ° C for 4 hours. The mixture was stirred at 120 ° C for 4 hours. Time. The mixture was stirred at 100 ° C for 1 hour. This mixture was cooled to room temperature, and 444 parts of chloroform and 300 parts of 1N hydrochloric acid were added and stirred, and then left to stand. The chloroform solution layer was extracted, washed twice with 300 parts of 1N hydrochloric acid, washed three times with 300 parts of a 15% sodium carbonate aqueous solution, and washed once with 300 parts of a 10% acetic acid aqueous solution. The chloroform solution layer was dried with magnesium sulfate, and then filtered. The solvent was distilled off from the filtrate by a rotary evaporator, and then dried under reduced pressure at 60 ° C. After adding 10.6 parts of acetone to the obtained residue and stirring, it was dropped into a mixture of 240 parts of water and 60 parts of methanol. To this mixture, 888 parts of chloroform was added and stirred, and then left to stand. The chloroform solution layer was extracted, dried over magnesium sulfate, and then filtered. The solvent was distilled off from the filtrate using a rotary evaporator. After adding 22.3 parts of N, N-dimethylformamide to the obtained residue and stirring, it was dropped into 610 parts of an 18% sodium chloride aqueous solution. Suction filtration was performed to obtain insoluble matter as a residue. This residue was dried under reduced pressure at 60 ° C to obtain 1.55 parts of a compound represented by the formula (I-118).

<Identification of compound represented by formula (I-118)>

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 636

Accurate quality: 635

Example 4

1.03 parts of the compound represented by the formula (I-96) obtained above, trimellitic anhydride (Manufactured by Tokyo Chemical Industry Co., Ltd.) 4.09 parts, 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.797 parts and 1-methyl-2-pyrrolidone (manufactured by Nacalai Tesque Co., Ltd.) 35.5 parts were mixed and stirred at 100 ° C for 6 hours. To this mixture were added 2.08 parts of trimellitic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.406 parts of 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.), and the mixture was stirred at 100 ° C for 2.5 hours. This mixture was cooled to room temperature, and 444 parts of chloroform and 300 parts of 1N hydrochloric acid were added and stirred, and then left to stand. The chloroform solution layer was extracted and washed 4 times with 300 parts of 1N hydrochloric acid. The solvent was distilled off from this chloroform solution using a rotary evaporator. 269 parts of ethyl acetate and 300 parts of 1N hydrochloric acid were added to the obtained residue, and after stirring, they were allowed to stand to extract an ethyl acetate solution layer. 300 parts of a 15% sodium carbonate aqueous solution was added to this ethyl acetate solution, and after stirring, it was left still, and the aqueous layer was extracted. To this aqueous solution was added 100 parts of a 15% sodium carbonate aqueous solution. 105 parts of 35% hydrochloric acid and 269 parts of ethyl acetate were added to this aqueous solution, and after stirring, they were allowed to stand, and the ethyl acetate solution layer was extracted. 300 parts of a 10% acetic acid aqueous solution was added to this ethyl acetate solution, and after stirring, it was allowed to stand, and the ethyl acetate solution layer was extracted. This ethyl acetate solution was dried with magnesium sulfate, and then filtered. The solvent was distilled off from the filtrate using a rotary evaporator. This residue was purified by column chromatography to obtain 0.354 parts of a mixture of the compound represented by the formula (I-119) and the compound represented by the formula (I-120).

<Identification of compound represented by formula (I-119)>

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 680

Accurate mass: 679

<Identification of compound represented by formula (I-120)>

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 680

Accurate mass: 679

Example 5

45.4 parts of 3-amino-4-hydroxybenzenesulfonic acid hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.), 9.50 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 4- (diethylamino) willow 44.1 parts of aldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 25.8 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 547 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed at 125 Stir at 2 ° C for 2 hours.

To this mixture were mixed 9.50 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 44.1 parts of 4- (diethylamino) salsal (manufactured by Tokyo Chemical Industry Co., Ltd.), and ethyl cyanoacetate (Tokyo Chemical Industry 25.8 parts of industrial (stock) and 30.3 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 125 ° C for 12 hours.

After cooling the mixture to room temperature, suction filtration was performed to obtain a solid form as a residue. Thing. 967 parts of N, N-dimethylformamide was added to this residue, and it stirred at 90 degreeC for 2 hours. The mixture was subjected to suction filtration while maintaining the mixture at 80 ° C. to obtain a solid substance as a suction filtration residue. To this residue was added 126 parts of N, N-dimethylformamide, and suction filtration was performed to obtain a solid substance as a residue.

967 parts of N, N-dimethylformamide was added to this residue, and it stirred at 90 degreeC for 4 hours. This mixture was stirred at room temperature for 12 hours and suction-filtered to obtain a solid substance as a residue. To this residue was added 126 parts of N, N-dimethylformamide, and suction filtration was performed to obtain a solid substance as a residue.

2000 parts of water was added to this residue, and it heated at 80 degreeC, and prepared the solution. After this solution was cooled to 30 ° C, 1580 parts of methanol was added and stirred for 12 hours. Suction filtration was performed to obtain a solid precipitate as a residue. 2000 parts of water was added to this residue, and it heated at 80 degreeC, and prepared the solution. The solvent of this solution was distilled off to obtain a solid substance.

148 parts of chloroform was added to this solid and stirred. The solvent of the mixture was removed by distillation to obtain 75.3 parts of a compound represented by the formula (1PAT).

<Identification of compound represented by formula (1PAT)>

¹ H-NMR (500MHz, DMSO-d ₆ ): 1.14 (6H, t), 3.49 (4H, q), 6.60 (1H, d), 6.81 (1H, dd), 7.09 (4H, s), 7.66 ( 1H, dd), 7.66 (1H, d), 7.70 (1H, d), 7.88 (1H, d), 8.83 (1H, s).

4.3 parts of the compound represented by formula (1PAT), 1.9 parts of N, N-dimethylformamide and 1,4-di 21 parts of alkane were mixed, and while stirring the mixture, 3.1 parts of phosphorus oxychloride was added dropwise at room temperature. Add 1,4-di to this mixture 10 parts of alkane were stirred at 70 ° C for 3 hours. To this mixture were added 3.1 parts of phosphorus oxychloride and 0.94 parts of N, N-dimethylformamide, and the mixture was stirred at 70 ° C for 1 hour. The mixture was left to cool to room temperature. Suction filtration was performed to obtain insoluble matter as a residue. The residue was washed with 16 parts of acetonitrile and air-dried. 5.6 parts of a residue was obtained.

2.1 parts of this residue and 1,4-di 5.2 parts of alkanes were mixed. While cooling the mixture with a water bath and stirring, 0.37 parts of DL-1-amino-2-propanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.0 part of triethylamine were added to the mixture. The mixture was stirred at room temperature for 2 hours. This mixture was added to 25 parts of water. Suction filtration was performed to obtain insoluble matter as a residue. This residue was dissolved in a mixed solution of 24 parts of N, N-dimethylformamide and 20 parts of methanol. The solvent was distilled off from this solution using a rotary evaporator. The obtained residue was purified by column chromatography. To the obtained crystals, 16 parts of hexane was added and stirred. This mixture was subjected to suction filtration and the obtained residue was air-dried to obtain 1.3 parts of a compound represented by the formula (I-10-1).

<Identification of compound represented by formula (I-10-1)>

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 472

Accurate quality: 471

Example 6

4.7 parts of the compound represented by formula (I-10-1), trimellitic anhydride (Tokyo Chemical Industry Co., Ltd.) (Manufactured) 9.6 parts, 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.7 parts and 1-methyl-2-pyrrolidone (manufactured by Nacalai Tesque (stock)) were mixed , And stirred at 100 ° C. for 1 hour under a nitrogen environment.

The mixture was left to cool to room temperature, and then filtered. After adding 90 parts of ethyl acetate and 160 parts of 10% hydrochloric acid to the filtrate and stirring them, the ethyl acetate solution layer was extracted. 160 parts of 10% hydrochloric acid was added to this ethyl acetate solution, and the mixture was left to stand, and then the ethyl acetate solution layer was extracted. To this ethyl acetate solution, 120 parts of a 15% sodium carbonate aqueous solution was added, stirred, and left to stand, and then the aqueous solution layer was extracted. 90 parts of ethyl acetate was added to this aqueous solution, and while stirring in an ice bath, 35% hydrochloric acid was added so that the pH of the aqueous layer did not reach 1. The mixture was left to stand, and an ethyl acetate solution layer was extracted. 150 parts of a 10% acetic acid aqueous solution was added to this ethyl acetate solution, and after stirring, it was left still, and the ethyl acetate solution layer was extracted. This ethyl acetate solution was dried with magnesium sulfate, and then filtered. The solvent was distilled off from the filtrate using a rotary evaporator. This residue was purified by column chromatography to obtain 4.9 parts of a mixture of the compound represented by the formula (I-33-1) and the compound represented by the formula (I-34-1).

[Chemical 47]

<Identification of compound represented by formula (I-33-1)>

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 664

Accurate quality: 663

<Identification of compound represented by formula (I-34-1)>

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 664

Accurate quality: 663

Synthesis Example 1

After passing a suitable amount of nitrogen into a flask equipped with a reflux cooler, a dropping funnel, and a stirrer to create a nitrogen atmosphere, 100 parts of propylene glycol monomethyl ether acetate was added and heated to 85 ° C while stirring. Next, 19 parts of methacrylic acid, {3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yl} ester, and 19 parts of methacrylic acid were dropped into the flask using a dropping pump over about 5 hours. 171 parts of a mixture of {3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9-yl} acrylate (containing a molar ratio of 50:50) dissolved in propylene glycol monomethyl ether ethyl 40 parts of the obtained solution. On the other hand, 26 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in propylene glycol monomethyl ether dropwise into the flask using another dropping pump over about 5 hours. A solution of 120 parts of acetate. After the completion of the addition of the polymerization initiator, the solution was kept at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin B1) having a solid content of 43.5%. The weight average molecular weight of the obtained resin B1 was 8000, the molecular weight distribution was 1.98, and the acid value in terms of solid content was 53 mgKOH / g.

[Measurement of film thickness]

The film thickness was measured using DEKTAK3 (manufactured by Japan Vacuum Technology Co., Ltd.).

[Preparation of resin composition (SJS) for sublimation test]

The following components were mixed to obtain a resin composition (SJS) for a sublimation test.

[Formation of Sublimation Test Resin Coating Film (SJSM)]

A 2 inch square glass substrate (EAGLE XG; manufactured by Corning) was applied by a spin coating method to obtain the sublimation test resin composition (SJS) obtained above, and the volatile components were made at 100 ° C for 3 minutes. Volatile. After cooling, light exposure was performed using an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) at an exposure amount (based on 365 nm) of 150 mJ / cm ² in the atmospheric environment. It heated at 220 degreeC in the oven for 2 hours, and formed the resin coating film (SJSM) for sublimation test (film thickness 2.2 micrometers).

Example 7

The following components were mixed to obtain a colored resin composition.

Example 8

The following components were mixed to obtain a colored resin composition.

Example 9

The following components were mixed to obtain a colored resin composition.

Comparative Example 1

The following components were mixed to obtain a colored resin composition.

[Sublimation evaluation]

Example 10

It was formed by applying the colored resin composition obtained in Example 7 to a 2-inch square glass substrate (EAGLE XG; manufactured by Corning) by a spin coating method, and then prebaking at 100 ° C for 3 minutes to form A colored resin composition layer. The film thickness was measured using DEKTAK3 (manufactured by Japan Vacuum Technology Co., Ltd.). This colored coating film and the resin coating film (SJSM) for a sublimation test obtained above were opposed to each other at a distance of 70 μm, and were baked at 220 ° C. for 40 minutes and then baked. The color difference (ΔEab *) of the resin coating film (SJSM) for sublimation test before and after heating was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS). If A color difference (ΔEab *) of 5.0 or more indicates that the colorant has sublimability. The results are shown in Table 9. In Table 9, ○ indicates that the colorant does not have sublimability, and X indicates that the colorant has sublimability.

Example 11

The coloring resin composition obtained in Example 7 was replaced with the coloring resin composition obtained in Example 8 and the sublimation property evaluation was performed in the same manner as in Example 10. The results are shown in Table 9.

Example 12

The coloring resin composition obtained in Example 7 was replaced with the coloring resin composition obtained in Example 9 and the sublimability evaluation was performed in the same manner as in Example 10. The results are shown in Table 9.

Comparative Example 2

The coloring resin composition obtained in Example 7 was replaced with the coloring resin composition obtained in Comparative Example 1, and the sublimability evaluation was performed in the same manner as in Example 10. The results are shown in Table 9.

[Preparation of colored resin composition]

Example 13

The following components were mixed to obtain a colored resin composition.

Colorant (A): 27 parts of CI Pigment Green 7 (Pigment),

Example 14

A colored resin composition was obtained in the same manner as in Example 13 except that C.I. Pigment Green 7 (pigment) of the colorant (A) was replaced with C.I. Pigment Green 36 (pigment).

Example 15

A colored resin composition was obtained in the same manner as in Example 13 except that C.I. Pigment Green 7 (pigment) of the colorant (A) was replaced with C.I. Pigment Green 58 (pigment).

Example 16

[Making of colored patterns]

It was formed by applying the colored resin composition obtained in Example 13 to a 2-inch square glass substrate (EAGLE XG; manufactured by Corning) by a spin coating method, followed by prebaking at 100 ° C for 3 minutes to form Coloring composition layer. After cooling, the distance between the substrate on which the coloring composition layer was formed and the mask made of quartz glass was set to 200 μm, and an exposure machine (TME-150RSK; manufactured by TOPCON) was used at 80 mJ / cm ² in an atmospheric environment. Exposure was performed at an exposure amount (based on 365 nm). In addition, as the photomask, a 100 μm line and gap pattern was used. The coloring composition layer after exposure was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C for 70 seconds to develop, and washed with water.

This colored coating film was baked at 230 ° C. for 30 minutes, thereby obtaining a colored pattern.

Example 17

A colored pattern was obtained in the same manner as in Example 16 except that the colored resin composition obtained in Example 13 was replaced with the colored resin composition obtained in Example 14.

Example 18

A colored pattern was obtained in the same manner as in Example 16 except that the colored resin composition obtained in Example 13 was replaced with the colored resin composition obtained in Example 15.

[Preparation of colored resin composition]

Example 19

The compound represented by the formula (I-117) was replaced by a mixture of the compound represented by the formula (I-119) obtained in Example 4 and the compound represented by the formula (I-120). Example 8 was performed in the same manner to obtain a colored resin composition.

Example 20

The compound represented by formula (I-117) was replaced with the compound represented by formula (I-10-1) obtained in Example 5. Except for the compound shown, it carried out similarly to Example 8, and obtained the coloring resin composition.

Example 21

Except replacing the compound represented by formula (I-117) with a mixture of the compound represented by formula (I-33-1) obtained in Example 6 and the compound represented by formula (I-34-1) In the same manner as in Example 8, a colored resin composition was obtained.

[Sublimation evaluation]

Example 22

The coloring resin composition obtained in Example 7 was replaced with the coloring resin composition obtained in Example 19, and the sublimability evaluation was performed in the same manner as in Example 10. The results are shown in Table 10.

Example 23

Sublimation property evaluation was performed in the same manner as in Example 10 except that the coloring resin composition obtained in Example 7 was replaced with the coloring resin composition obtained in Example 20. The results are shown in Table 10.

Example 24

Sublimation evaluation was performed in the same manner as in Example 10 except that the colored resin composition obtained in Example 7 was replaced with the colored resin composition obtained in Example 21. The results are shown in Table 10.

[Preparation of colored resin composition]

Example 25

A colored resin composition was obtained in the same manner as in Example 13 except that C.I. Pigment Green 7 (pigment) of the colorant (A) was replaced with C.I. Pigment Green 59 (pigment).

Example 26

[Making of colored patterns]

A colored pattern was obtained in the same manner as in Example 16 except that the colored resin composition obtained in Example 13 was replaced with the colored resin composition obtained in Example 25.

Example 27

In Example 3, except having replaced phthalic anhydride with tetrachlorophthalic anhydride, it implemented similarly to Example 3, and obtained the compound represented by Formula (I-122).

Example 28

In Example 6, except having replaced trimellitic anhydride with tetrachlorophthalic anhydride, it was carried out in the same manner as in Example 6 to obtain a compound represented by the formula (I-36-1).

Example 29

In Example 3, except having replaced phthalic anhydride with tetrafluorophthalic anhydride, it implemented similarly to Example 3, and obtained the compound represented by Formula (I-121).

Example 30

In Example 6, except having replaced trimellitic anhydride with tetrafluorophthalic anhydride, it was carried out in the same manner as in Example 6 to obtain a compound represented by the formula (I-35-1).

Example 31

In Example 5, except that 4- (diethylamino) salixal was replaced with 4- (dioctylamino) salixal, the same procedure as in Example 5 was performed to obtain formula (I -53-1).

Example 32

In Example 6, the compound represented by the formula (I-10-1) was replaced with the compound represented by the formula (I-53-1), and trimellitic anhydride was replaced with phthalic acid. A compound represented by the formula (I-75-1) was obtained in the same manner as in Example 6.

Based on the above results, it was confirmed that the present invention can provide a colored resin composition capable of forming a color filter in which the sublimation of the colored agent is suppressed.

[Industrial availability]

According to the present invention, a compound that can be used as a colorant for a color filter can be obtained. The compound is easy to synthesize and can be manufactured without a dimerization step. A coloring resin composition capable of forming a color filter in which the sublimation of the coloring agent is suppressed can be provided. The color filter is suitable for a display device such as a liquid crystal display device.

Claims (12)

A compound, which is represented by formula (I),

[In formula (I), X represents an oxygen atom or a sulfur atom; R ¹ and R ² each independently represent a hydrocarbon group having 1 to 20 carbon atoms; n represents an integer of 1 to 4; A represents -SO ₂ -NR ³ -L ² -OCO-L ³ -CO-OM; M represents a hydrogen atom or an alkali metal atom; in the presence of a plurality of M, they may be the same or different from each other; L ² and L ³ each independently represent a carbon number of 1 to 30 Divalent hydrocarbon group; -CH = constituting the divalent hydrocarbon group may be substituted with -N =, -CH ₂ -constituting the divalent hydrocarbon group may be substituted with oxygen atom, sulfur atom, -N (R ⁵⁵ )-, sulfonate Acyl group or carbonyl group, the hydrogen atom contained in the divalent hydrocarbon group can be replaced with a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, -SO ₃ M ³ , -CO ₂ M ³ , hydroxyl group 、 Methyl or amine groups; R ⁵⁵ represents a hydrogen atom or a monovalent hydrocarbon group with a carbon number of 1 to 20; in the presence of a plurality of R ⁵⁵ , they can be the same or different from each other; R ³ represents a hydrogen atom, carbon number 1-20 monovalent hydrocarbon group or a group represented by formula (z); the hydrogen atom contained in the monovalent hydrocarbon group may be replaced by a halogen atom, a hydroxyl group or a carboxyl group, and -CH ₂ -constituting the monovalent hydrocarbon group may be substituted Is a carbonyl group; in the presence of a plurality of R ³ , they can be mutually Same or different;

In formula (z), L ²² and L ³³ each independently represent a divalent hydrocarbon group having 1 to 30 carbon atoms; -CH = constituting the divalent hydrocarbon group may be substituted with -N =, -CH ₂ constituting the divalent hydrocarbon group -It can be substituted with oxygen atom, sulfur atom, -N (R ⁴⁴ )-, sulfonyl group or carbonyl group, the hydrogen atom contained in the divalent hydrocarbon group can be replaced with halogen atom, cyano group, nitro group, carbamoyl group Group, sulfamoyl group, -SO ₃ M ³ , -CO ₂ M ³ , hydroxyl group, methyl group or amine group; M ¹ represents a hydrogen atom or an alkali metal atom; in the presence of a plurality of M ¹ , etc. may be the same or different from each other; substituents L ^1, -SO ^₃ M ₃ or -CO ₂ M ³ of the hydrogen atoms contained in L ^2, L ^3, L ²² or L ³³ of the divalent hydrocarbon group contained in the M ³ represents a hydrogen atom Or an alkali metal atom; in the presence of multiple M ³ , they may be the same as or different from each other; R ⁴⁴ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; in the presence of multiple R ⁴⁴ , its Etc. may be the same or different from each other]. If the compound of claim 1, it is represented by formula (II), [Chem 3]

[In formula (II), n, X, R ¹ , R ² , L ² and L ³ each have the same meaning as described above; R ³³ represents a hydrogen atom or -L ²² -OCO-L ³³ -CO ₂ M ² ; L ²² and L ³³ each have the same meaning as described above; M ² represents a hydrogen atom or an alkali metal atom; in the case where a plurality of M ² are present, they may be the same or different from each other]. The compound according to claim 1 or 2, wherein the above L ²² is a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the above L ³³ is a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group which may be substituted with a carboxyl group or a halogen atom. The compound according to claim 1 or 2, wherein the above L ² is a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the above L ³ is a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group which may be substituted with a carboxyl group or a halogen atom. The compound according to claim 3, wherein the above L ² is a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the above L ³ is a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group which may be substituted with a carboxyl group or a halogen atom. The compound according to claim 1 or 2, wherein the above R ¹ and R ² are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms. The compound according to claim 3, wherein R ¹ and R ² are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms. The compound according to claim 4, wherein R ¹ and R ² are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms. The compound according to claim 5, wherein each of R ¹ and R ^{2 is} independently a monovalent hydrocarbon group having 1 to 10 carbon atoms. A coloring resin composition containing a coloring agent, a resin, a polymerizable compound, a polymerization initiator, and a solvent containing the compound of any one of claims 1 to 9. A color filter formed of the coloring resin composition according to claim 10. A liquid crystal display device comprising the color filter according to claim 11.