WO2016039405A1 - Compound, and colored curable resin composition including said compound - Google Patents

Abstract

　The present invention provides a compound with which it is possible to suppress sublimation of colorant when forming a color filter from a colored curable resin composition. A compound represented by formula (Z). (In formula (Z), R¹ and R² each independently represent a hydrogen atom, a C1-20 monovalent saturated hydrocarbon group, an aryl group, a group including an acryloyl group, a group including a methacryloyl group, or a group including a silicon atom. R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ each independently represent a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, a nitro group, a C1-20 alkyl group, a C1-20 alkoxy group, a group including an acryloyl group, a group including a methacryloyl group, or a group including a silicon atom. However, at least one among R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ is a group including an acryloyl group, a group including a methacryloyl group, or a group including a silicon atom.)

Description

Compound and colored curable resin composition containing the compound

The present invention relates to a compound, a colorant containing the compound, a colored curable resin composition, and the like.

Dyes are used for color display using reflected light or transmitted light in the fields of fiber materials, liquid crystal display devices, ink jets, and the like. As such a dye, coumarin 6 represented by the following formula is known.

JP 2006-154740 A (Example 8)

In the step of forming a color filter from a colored curable resin composition containing a compound represented by the formula (d0), the problem was that the colorant sublimated.

The present invention includes the following inventions.
[1] A compound represented by the formula (Z).

[In Formula (Z), R ¹ and R ² each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a group containing an acryloyl group, or a group containing a methacryloyl group. Or represents a group containing a silicon atom.
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, a nitro group, or a carbon number of 1 to 20 An alkyl group having 1 to 20 carbon atoms, a group containing an acryloyl group, a group containing a methacryloyl group, or a group containing a silicon atom.
Provided that at least ^one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is a group containing an acryloyl group, a group containing a methacryloyl group, or It is a group containing a silicon atom. ]
[2] The compound according to [1], wherein the group containing a silicon atom is a group represented by the formula (Z1).

[Wherein R ^11A represents a single bond or an alkanediyl group having 1 to 10 carbon atoms, and —CH ₂ — contained in the alkanediyl group represents —O—, —CO—, —NR ¹⁰ —, — OCO—, —COO—, —OCONH—, —CONH— or —NHCO— may be substituted, and the hydrogen atom contained in the alkanediyl group may have a hydroxyl group of 1 to 4 carbon atoms. The alkyl group may be substituted.
R ¹⁰ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
R ^12A , R ^13A and R ^14A each independently represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
* Represents a bond with a nitrogen atom or a carbon atom. ]
[3] The compound according to [1] or [2], wherein the group containing an acryloyl group or the group containing a methacryloyl group is a group represented by the formula (Z2).

[Wherein R ^15A represents an alkanediyl group having 1 to 10 carbon atoms, and —CH ₂ — contained in the alkanediyl group represents —O—, —CO—, —NR ¹¹ —, —OCO—, The hydrogen atom contained in the alkanediyl group may be substituted with —COO—, —OCONH—, —CONH— or —NHCO—, and the alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group May be substituted.
R ¹¹ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
R ^16A represents an acryloyl group or a methacryloyl group.
* Represents a bond with a nitrogen atom or a carbon atom. ]
[4] A colorant comprising the compound according to any one of [1] to [3].
[5] The colorant according to [4], further comprising a green pigment.
[6] The colorant according to [5], wherein the green pigment is at least one selected from the group consisting of a halogenated copper phthalocyanine pigment and a halogenated zinc phthalocyanine pigment.
[7] The colorant according to [5] or [6], wherein the green pigment is at least one selected from the group consisting of a chlorinated copper phthalocyanine pigment, a brominated copper phthalocyanine pigment, and a brominated zinc phthalocyanine pigment.
[8] The green pigment is C.I. I. Pigment green 36 and C.I. I. The colorant according to any one of [5] to [7], which is at least one selected from the group consisting of CI Pigment Green 58.
[9] A colored curable resin composition comprising the colorant, resin, polymerizable compound and polymerization initiator according to any one of [4] to [8].
[10] A color filter formed from the colored curable resin composition according to [9].
[11] A liquid crystal display device including the color filter according to [10].

When forming a color filter from a colored curable resin composition containing the compound of the present invention, sublimation of the colorant can be suppressed.

<Compound represented by formula (Z) (hereinafter sometimes referred to as compound (Z))>

[In Formula (Z), R ¹ and R ² each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a group containing an acryloyl group, or a group containing a methacryloyl group. Or represents a group containing a silicon atom.
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, a nitro group, or a carbon number of 1 to 20 An alkyl group having 1 to 20 carbon atoms, a group containing an acryloyl group, a group containing a methacryloyl group, or a group containing a silicon atom.
Provided that at least ^one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is a group containing an acryloyl group, a group containing a methacryloyl group, or It is a group containing a silicon atom. ]

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. A linear alkyl group having 1 to 20 carbon atoms such as n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-hexadecyl group and icosyl group; isopropyl group A branched alkyl group having 3 to 20 carbon atoms such as isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; alkyl group having 1 to 20 carbon atoms such as
Examples thereof include alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group.
Examples of the aryl group represented by R ¹ and R ² include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2, Alkyl such as 5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group Examples thereof include a phenyl group which may be substituted, preferably a tolyl group or a dimethylphenyl group.

R ¹ and R ² are each independently preferably an alkyl group having 1 to 20 carbon atoms, more preferably a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 5 to 10 carbon atoms, An ethyl group or 2-ethylhexyl group is more preferable, and an ethyl group is still more preferable.

* —NR ¹ R ² (* represents a bond to a carbon atom) is preferably a group represented by the following formula.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ include a methyl group, ethyl group, n-propyl group, isopropyl Group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and methylcyclohexyl group Is mentioned.

Examples of the alkoxy group having 1 to 20 carbon atoms represented by R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, Examples include a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group.

Examples of the halogen atom represented by R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ include a fluorine atom, a chlorine atom and a bromine atom.

Provided that at least ^one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is a group containing an acryloyl group, a group containing a methacryloyl group, or It is a group containing a silicon atom.

A group containing an acryloyl group or a group containing a methacryloyl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is a group structure. The unit means a group having at least one acryloyl group or methacryloyl group.
The number of carbon atoms of the group containing an acryloyl group is usually 3 to 16, preferably 3 to 12, and more preferably 3 to 8.
The number of carbon atoms of the group containing a methacryloyl group is usually 4 to 17, preferably 4 to 13, and more preferably 4 to 9.
The group containing an acryloyl group is preferably a group containing an acryloyloxy group.
The group containing a methacryloyl group is preferably a group containing a methacryloyloxy group.
The group containing an acryloyl group or the group containing a methacryloyl group is preferably a group represented by the formula (Z2).

[Wherein R ^15A represents an alkanediyl group having 1 to 10 carbon atoms, and —CH ₂ — contained in the alkanediyl group represents —O—, —CO—, —NR ¹¹ —, —OCO—, The hydrogen atom contained in the alkanediyl group may be substituted with —COO—, —OCONH—, —CONH— or —NHCO—, and the alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group May be substituted.
R ¹¹ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
R ^16A represents an acryloyl group or a methacryloyl group.
* Represents a bond with a nitrogen atom or a carbon atom. ]

^Examples of the alkanediyl group having 1 to 10 carbon atoms represented by R ^15A include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, isopropylene group, isobutylene group, 2-methyltrimethyl group. Examples include a methylene group, an isopentylene group, an isohexylene group, an isooctylene group, and a 2-ethylhexylene group, preferably an alkanediyl group having 1 to 6 carbon atoms, and more preferably an alkanediyl group having 1 to 4 carbon atoms.
The alkanediyl group having 1 to 10 carbon atoms represented by R ^15A is preferably a group in which —CH ₂ — contained in the alkanediyl group is substituted with —O—. The number of —O— in R ^15A is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1. At least one of the —O— may be bonded to R ^16A . Note -CH ₂ - a nitrogen atom or a bond carbon atoms _* -CH 2 of the - ^{is, -O -, - CO -,} - NR 11 -, - OCO -, - COO -, - OCONH -, - It is preferably not substituted with CONH- and -NHCO-.
Examples of the alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , A methyl group, an ethyl group, a propyl group or a butyl group is preferable, and an ethyl group is more preferable.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹¹ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group. An alkyl group having 1 to 20 carbon atoms such as a group, dodecyl group, hexadecyl group, icosyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group;
Examples thereof include alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group.
R ¹¹ is preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and more preferably a methyl group or a hydrogen atom.

Examples of the group containing an acryloyl group or a methacryloyl group include a group represented by (ii-1) to a group represented by (ii-42), preferably a group represented by (ii-1) A group represented by (ii-8) and a group represented by (ii-13) to a group represented by (ii-22), more preferably a group represented by (ii-1) to ( a group represented by ii-8), more preferably a group represented by (ii-1) or a group represented by (ii-5). In the formula, * represents a bond.

The group containing a silicon atom represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ includes a silicon atom as a component of the group. Means group.
The number of carbon atoms of the group containing a silicon atom is usually 1 to 30, preferably 1 to 20, and more preferably 1 to 10.
The group containing a silicon atom is preferably a group represented by the formula (Z1).

[Wherein R ^11A represents a single bond or an alkanediyl group having 1 to 10 carbon atoms, and —CH ₂ — contained in the alkanediyl group represents —O—, —CO—, —NR ¹⁰ —, — OCO—, —COO—, —OCONH—, —CONH— or —NHCO— may be substituted, and the hydrogen atom contained in the alkanediyl group may have a hydroxyl group of 1 to 4 carbon atoms. The alkyl group may be substituted.
R ¹⁰ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
R ^12A , R ^13A and R ^14A each independently represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
* Represents a bond with a nitrogen atom or a carbon atom. ]

^Examples of the alkanediyl group having 1 to 10 carbon atoms represented by R ^11A include the same as the alkanediyl group having 1 to 10 carbon atoms represented by R ^15A . R ^11A is preferably an alkanediyl group having 1 to 6 carbon atoms, and more preferably an alkanediyl group having 1 to 4 carbon atoms.
^Examples of the alkyl group having 1 to 4 carbon atoms that may replace the hydrogen atom of the alkanediyl group of R ^11A include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert group. -Butoxy group.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁰ include the same as the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹¹ .

^Examples of the alkyl group having 1 to 4 carbon atoms represented by R ^12A , R ^13A and R ^14A include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Group, cyclopropyl group and cyclobutyl group.
^Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ^12A , R ^13A and R ^14A include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group and a tert-butoxy group. Is mentioned.
R ^12A , R ^13A and R ^14A are preferably all the same group.
R ^12A , R ^13A and R ^14A are each independently preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and an alkyl group having 1 to 2 carbon atoms or 1 carbon atom An alkoxy group of ˜2 is more preferred, and a methyl group is still more preferred.

Examples of the group containing a silicon atom include the groups described below. ^{Examples of the group in} which R ^11A is not a single bond or —CH ₂ — contained in R ^11A are substituted include the groups shown below (* represents a bond).

^Examples of the group in which —CH ₂ — contained in R ^11A is substituted with —O— include the groups shown below (* represents a bond).

Examples of the group in which —CH ₂ — contained in R ^11A is substituted with —CO— include the groups shown below (* represents a bond).

The group in which —CH ₂ — contained in R ^11A is substituted with —NR ¹⁰ — is preferably —NH—, —NCH ₃ —, —NC ₂ H ₅ —, and preferred groups are the groups shown below: (* Represents a bond).

Examples of the group in which —CH ₂ — contained in R ^11A is substituted with —OCO— include the groups shown below (* represents a bond).

Examples of the group in which —CH ₂ — contained in R ^11A is substituted with —COO— include the groups shown below (* represents a bond).

Examples of the group in which —CH ₂ — contained in R ^11A is substituted with —OCONH— include the following groups (* represents a bond).

Examples of the group in which —CH ₂ — contained in R ^11A is substituted with —CONH— include the groups shown below (* represents a bond).

Examples of the group in which —CH ₂ — contained in R ^11A is substituted with —NHCO— include the groups shown below (* represents a bond).

Examples of the group in which the hydrogen atom contained in the alkanediyl group contained in R ^11A may be substituted with an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group include the following groups: (* Represents a bond).

The group containing a silicon atom is represented by the formula (Z1) in which —CH ₂ — contained in the alkanediyl group represented by R ^11A is substituted with —OCO—, —COO— or —OCONH—. A group represented by the formula (Z1) in which —CH ₂ — contained in the alkanediyl group represented by R ^11A is substituted with —COO— is more preferred. The group containing a silicon atom is preferably a group represented below.

R ³ , R ⁴ , R ⁵ and R ⁶ are each independently preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. More preferably, it is more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a carboxyl group, and preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a carboxyl group. It is more preferably a group, and further preferably a hydrogen atom or a carboxyl group.
It is preferable that at least one of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is a group containing an acryloyl group, a group containing a methacryloyl group or a group containing a silicon atom, and R ⁷ , R ⁸ , R ⁹ and R It is preferable that any one of ¹⁰ is a group containing an acryloyl group, a group containing a methacryloyl group, or a group containing a silicon atom.
The at least one of R ⁸ and R ^9, a group containing an acryloyl group is preferably a group containing a group or a silicon atom containing methacryloyl group, R ⁷ and R ¹⁰ are hydrogen atoms, R ⁸ and It is preferable that at least one of R ⁹ , more preferably any one of R ^{8 and} R ⁹ is a group containing an acryloyl group, a group containing a methacryloyl group, or a group containing a silicon atom.

Specific examples of the compound (Z) include a compound represented by the formula (Z-1) to a compound represented by the formula (Z-56).

Compound (Z) is, for example, Dyes and Pigments (2008), 77, 556-558. Can be produced according to the method described in 1. above.
Specifically, the compound represented by the formula (Z) in which R ⁵ = hydrogen atom includes a compound represented by the formula (2-A), a compound represented by the formula (2-B), and ethyl cyanoacetate. Can be produced by cyclization reaction in the presence of benzoic acid and a solvent.
The reaction temperature is preferably 0 ° C. to 200 ° C., more preferably 100 ° C. to 150 ° C. The reaction time is preferably 1 hour to 24 hours, more preferably 8 hours to 16 hours. Examples of the solvent include methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, and N-methylpyrrolidone, and 1-pentanol is preferable.

[In the formulas (2-A) and (2-B), R ¹ to R ⁴ and R ⁶ to R ¹⁰ each have the same meaning as described above. ]

The amount of the compound represented by the formula (2-A) to be used is preferably 1 mol to 10 mol, more preferably 1 to 5 mol, relative to 1 mol of the compound represented by the formula (2-B). And more preferably 1 mole.
The amount of ethyl cyanoacetate to be used is preferably 1 to 10 mol, more preferably 1 to 5 mol, still more preferably 1 mol with respect to 1 mol of the compound represented by the formula (2-B). It is.
The amount of benzoic acid to be used is preferably 0.1 mol to 3 mol, more preferably 0.3 to 0.4 mol, per 1 mol of the compound represented by the formula (2-B).
After obtaining the compound represented by the formula (Z) where R ⁵ = hydrogen atom, an arbitrary substituent may be introduced into R ⁵ using a known method.

Examples of the method for obtaining the compound represented by the formula (Z), which is the target compound, from the reaction mixture include a method of appropriately adjusting the temperature of the reaction mixture to precipitate crystals and collecting the crystals by filtration. The crystals collected by filtration were water, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, tetrahydrofuran, acetone, acetic acid, ethyl acetate, hexane, toluene, N, N-dimethylformamide. It is preferable to wash with a solvent such as N-methylpyrrolidone or a mixture thereof and then dry. Moreover, you may refine | purify further by well-known methods, such as column chromatography or recrystallization, as needed.

Further, for example, the compound (Z) in which R ⁹ is a group containing a silicon atom can be obtained by reacting a compound represented by the formula (z5a) with a compound represented by the formula (z6). The compound represented by the formula (z5a) can be produced by diazo coupling a compound represented by the formula (2-A) and a compound represented by the formula (z4a).
Similarly, the compound (Z) in which R ⁸ is a group containing a silicon atom can be obtained by reacting a compound represented by the formula (z5b) with a compound represented by the formula (z6). The compound represented by the formula (z5b) can be produced by diazo coupling the compound represented by the formula (2-A) and the compound represented by the formula (z4b).
Note that in this specification, the compound represented by the formula (z5a) and the compound represented by the formula (z5b) may be collectively referred to as a compound represented by the formula (z5).

[Wherein R ¹¹³ represents a divalent linking group.
R ¹¹⁴ and R ¹¹⁵ each independently represent a hydrophilic group.
R ¹¹⁶ represents a group containing a silicon atom.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represent the same meaning as described above. ]

^Examples of the divalent linking group represented by R ¹¹³ include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, isopropylene group, isobutylene group, 2-methyltrimethylene group, isopentylene. And an alkanediyl group having 1 to 10 carbon atoms such as an isohexylene group, an isooctylene group and a 2-ethylhexylene group. —CH ₂ — contained in the alkanediyl group is substituted with —O—, —CO—, —NR ¹⁰ —, —OCO—, —COO—, —OCONH—, —CONH— or —NHCO—. Also good. R ¹⁰ represents the same meaning as described above.
Examples of the hydrophilic group represented by R ¹¹⁴ and R ¹¹⁵ include a hydroxy group and a carboxy group. However, R ¹¹⁴ and R ¹¹⁵ do not represent the same group, and it is preferable that R ¹¹⁴ is a carboxyl group and R ¹¹⁵ is a hydroxyl group.
The group containing a silicon atom represented by R ¹¹⁶ represents a group containing a silicon atom as a component of the group, and is preferably a group represented by the formula (Z1).

[Wherein, R ^11A , R ^12A , R ^13A and R ^14A represent the same meaning as described above.
* Represents a bond to ^{R 115.} ]
A group represented by * —R ¹¹³ —R ¹¹⁶ (* represents a bond to a carbon atom) corresponds to R ⁸ and R ⁹ in the compound (Z).

The reaction between the compound represented by the formula (z5) and the compound represented by the formula (z6) is preferably performed in the presence of a halogenated solvent such as chloroform. The reaction temperature is preferably −10 ° C. to 100 ° C., more preferably 0 ° C. to 50 ° C. The reaction time is preferably 1 to 12 hours, more preferably 1 to 4 hours.

The usage-amount of the compound represented by a formula (z6) is 1 mol or more and 8 mol or less normally with respect to 1 mol of compounds represented by a formula (z5), Preferably they are 1 mol or more and 4 mol or less.
In the reaction, it is more preferable to add an acidic catalyst so that the reaction proceeds smoothly.
Examples of the acidic catalyst include mineral acids such as sulfuric acid and hydrochloric acid.
The amount of these catalysts to be used is arbitrary, but is preferably 0.01 to 4 mol, more preferably 0.8 to 2 mol, relative to 1 mol of the compound represented by the formula (z6).

Examples of the method for obtaining the target compound of the present invention from the reaction mixture include a method in which the reaction mixture is mixed with an acid (for example, acetic acid) and water, and the precipitated crystals are collected by filtration. The acid is preferably prepared by preparing an aqueous solution of the acid in advance, and then adding the reaction mixture to the aqueous solution. The temperature when adding the reaction mixture is usually 10 ° C. or higher and 50 ° C. or lower, preferably 20 ° C. or higher and 50 ° C. or lower, more preferably 20 ° C. or higher and 30 ° C. or lower. Further, after adding the reaction mixture to the aqueous acid solution, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystal collected by filtration is preferably washed with water or the like and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

For example, the compound (Z) in which R ⁹ is a group containing an acryloyl group or a group containing a methacryloyl group is obtained by reacting a compound represented by the formula (z8a) with a compound represented by the formula (z9). Can be obtained. The compound represented by the formula (z8a) can be produced by reacting the compound represented by the formula (2-A) with the compound represented by the formula (z7a).
The compound (Z) in which R ⁹ is a group containing an acryloyl group or a group containing a methacryloyl group can be obtained by reacting a compound represented by the formula (z8b) with a compound represented by the formula (z9). it can. The compound represented by the formula (z8b) can be produced by reacting the compound represented by the formula (2-A) with the compound represented by the formula (z7b).
Note that in this specification, the compound represented by the formula (z8a) and the compound represented by the formula (z8b) may be collectively referred to as a compound represented by the formula (z8).

[Wherein, R ¹¹¹ represents a divalent linking group.
R ¹¹⁰ represents a group containing an acryloyl group or a group containing a methacryloyl group.
R ¹¹² represents a halogen atom.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represent the same meaning as described above. ]

^Examples of the divalent linking group represented by R ¹¹¹ include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, isopropylene group, isobutylene group, 2-methyltrimethylene group, isopentylene. And an alkanediyl group having 1 to 10 carbon atoms such as an isohexylene group, an isooctylene group and a 2-ethylhexylene group. —CH ₂ — contained in the alkanediyl group is substituted with —O—, —CO—, —NR ¹¹ —, —OCO—, —COO—, —OCONH—, —CONH— or —NHCO—. Also good. R ¹¹ represents the same meaning as described above.
Examples of the halogen atom represented by R ¹¹² include a chlorine atom and a bromine atom.
Examples of the group containing an acryloyl group or a group containing a methacryloyl group represented by R ¹¹⁰ include a group having at least one acryloyl group or methacryloyl group as a structural unit of the group.
A group represented by * —R ¹¹¹ —R ¹¹⁰ (* represents a bond to a carbon atom) corresponds to R ⁸ and R ⁹ in the compound (Z).

The reaction between the compound represented by the formula (z8) and the compound represented by the formula (z9) is preferably performed in the presence of a halogenated solvent such as chloroform. The reaction temperature is preferably −10 ° C. to 100 ° C., more preferably 0 ° C. to 50 ° C. The reaction time is preferably 1 to 12 hours, more preferably 1 to 4 hours.

The usage-amount of the compound represented by a formula (z9) is 1 mol or more and 8 mol or less normally with respect to 1 mol of compounds represented by a formula (z8), Preferably they are 1 mol or more and 4 mol or less.
In the reaction, it is more preferable to add an acidic catalyst so that the reaction proceeds smoothly. Examples of the acidic catalyst include mineral acids such as sulfuric acid and hydrochloric acid.
The amount of these catalysts to be used is arbitrary, but is preferably 0.01 to 4 mol, more preferably 0.8 to 2 mol, relative to 1 mol of the compound represented by the formula (z9).

Examples of the method for obtaining the compound of the present invention that is the target compound from the reaction mixture include the same methods as those for obtaining the compound (Z) in which R ⁸ or R ⁹ is a group containing a silicon atom.

The compound (Z) of the present invention can be used as a dye.

The colored curable resin composition of the present invention includes a colorant (A) containing the compound (Z), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).
As the colorant (A), two or more compounds (Z) may be used. The colorant (A) may use a dye other than the compound (Z) or a green pigment (P).
The colored curable resin composition of the present invention preferably further contains at least one selected from the group consisting of a solvent (E) and a leveling agent (F).
The colored curable resin composition of the present invention may further contain a polymerization initiation assistant (D1).
In this specification, unless otherwise indicated, the compound illustrated as each component can be used individually or in combination of multiple types.

As the dye other than the compound (Z), a yellow dye or a red dye is preferable, and a yellow dye is particularly preferable. Examples of yellow dyes include dyes having a pyridone skeleton.

As the green pigment (P), halogenated copper phthalocyanine pigments such as fluorinated copper phthalocyanine pigments, chlorinated copper phthalocyanine pigments, brominated copper phthalocyanine pigments; fluorinated zinc phthalocyanine pigments, chlorinated zinc phthalocyanine pigments, brominated zinc phthalocyanine pigments Zinc halide phthalocyanine pigments such as C.I. I. And green pigments such as CI Pigment Green 7, 10, 15, 25, 36, 47, and 58.
The green pigment (P) is preferably at least one selected from the group consisting of a halogenated copper phthalocyanine pigment and a halogenated zinc phthalocyanine pigment,
More preferably, it is at least one selected from the group consisting of chlorinated copper phthalocyanine pigments, brominated copper phthalocyanine pigments and brominated zinc phthalocyanine pigments,
C. I. More preferably, it is at least one selected from the group consisting of CI Pigment Green 36 and 58.
Since the color difference after the sublimation test is small, the green pigment (P) is preferably a halogenated copper phthalocyanine pigment, more preferably at least one selected from the group consisting of a chlorinated copper phthalocyanine pigment and a brominated copper phthalocyanine pigment. , C.I. I. Pigment Green 36 is more preferable.

The colorant (A) may contain other pigments, for example,
Specifically, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 180, 194, 214;
C. I. And blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60, and the like.

The content of the compound (Z) is preferably 0.01% by mass or more and 90% by mass or less, more preferably 0.1% by mass or more and 80% by mass or less, with respect to the total amount of the colorant (A). More preferably, it is 1 mass% or more and 65 mass% or less, More preferably, it is 2 mass% or more and 60 mass% or less.
When the green pigment (P) is included, the content is preferably 10% by mass or more and 99.99% by mass or less, and more preferably 20% by mass or more and 99.9% by mass with respect to the total amount of the colorant (A). It is not more than mass%, more preferably not less than 35 mass% and not more than 99 mass%, and still more preferably not less than 40 mass% and not more than 98 mass%.
When the green pigment (P) is contained, the content ratio of the compound (Z) and the green pigment (P) [compound (Z): green pigment (P)] is preferably 1:99 to 50:50, more preferably 2:98 to 30:70, more preferably 3:97 to 20:80.

The total content of the compound (Z) and the green pigment (P) is preferably 10% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more with respect to the total amount of the colorant (A). Further, it is more preferably 70% by mass or more, particularly preferably 80% by mass or more, and the upper limit is 100% by mass or less, and may be 95% by mass or less.

The content of the colorant (A) is usually 1% by mass or more and 99% by mass or less, preferably 2% by mass or more and 90% by mass or less, with respect to the total solid content of the colored curable resin composition. More preferably, it is 3 mass% or more and 80 mass% or less, More preferably, it is 5 mass% or more and 70 mass% or less, More preferably, it is 5 mass% or more and 60 mass% or less, Most preferably, it is 5 mass%. It is 50 mass% or less. When the content of the colorant (A) is within the above range, a desired spectrum and color density can be obtained.

As used herein, “total amount of solids” refers to the total amount of components obtained by removing the solvent (E) from the colored curable resin composition of the present invention. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and an addition polymer having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. More preferred. Examples of such resins include the following resins [K1] to [K6].
Resin [K1] At least one (a) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a)”), a cyclic ether structure having 2 to 4 carbon atoms, A copolymer with a monomer (b) having an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”);
Resin [K2] (a) and (b), monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter referred to as “(c)”) In some cases)
Resin [K3] Copolymer of (a) and (c);
Resin [K4] A resin obtained by reacting (b) with a copolymer of (a) and (c);
Resin [K5] A resin obtained by reacting (a) with a copolymer of (b) and (c);
Resin [K6] A resin obtained by reacting (a) with a copolymer of (b) and (c) and further reacting with a carboxylic acid anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an alkaline aqueous solution.

(B) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Say. (B) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”), etc. Can be mentioned.

Examples of (b1) include a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”) And a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).

(B1-1) includes glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6- Examples include tris (glycidyloxymethyl) styrene.

Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), a formula Examples thereof include a compound represented by (I) and a compound represented by formula (II).

[In the formulas (I) and (II), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. May be.
X ^a and ^{X b} is a single ^{bond, * - R c -, *} - R c -O -, * - represents the R c -S- or ^* -R c -NH-.
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

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

Examples of alkanediyl groups include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- Examples include 1,6-diyl group.
X ^a and X ^b are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— and * —CH ₂ CH ₂ —O—, more preferably a single bond, * —CH _2. CH ₂ —O— (* represents a bond with O).

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

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

The compound represented by formula (I) and the compound represented by formula (II) may be used alone or in combination with the compound represented by formula (I) and the compound represented by formula (II). May be. When these are used in combination, the content ratio of the compound represented by formula (I) and the compound represented by formula (II) is preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, more preferably 20:80 to 80:20.

(B2) is more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. (B2) includes 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane , 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

(B3) is more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

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

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in the art, it is commonly referred to as “dicyclopentanyl (meth) acrylate”. In the case of “tricyclodecyl (meth) acrylate”) There is a bird) Black (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) [5.2.1.0 ^2,6] decene-8-yl (meth) acrylate, dicyclopenta Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylic acid esters of
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Of these, styrene, vinyltoluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, N from the viewpoint of copolymerization reactivity and heat resistance. -Phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable.

In the resin [K1], the ratio of the structural unit derived from each is the total structural unit constituting the resin [K1]
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (b); 40 to 98 mol%
It is preferable that
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (b); 50 to 90 mol%
It is more preferable that
When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter are excellent. Tend.

Resin [K1] is, for example, a method described in the document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) and the document Can be produced with reference to the cited references described in 1.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, for example, by substituting oxygen with nitrogen to create a deoxygenated atmosphere, with stirring, The method of heating and heat retention is mentioned. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and those usually used in the field can be used. For example, as polymerization initiators, azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) As the solvent, any solvent that dissolves each monomer may be used. Examples of the solvent (E) for the colored curable resin composition of the present invention include a solvent described later.

In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during the polymerization, the solution after the reaction is used as it is for the preparation of the colored curable resin composition of the present invention. Therefore, the manufacturing process of the colored curable resin composition of the present invention can be simplified.

In the resin [K2], the ratio of the structural units derived from each of the structural units in the resin [K2]
Structural unit derived from (a); 2 to 45 mol%
Structural unit derived from (b); 2 to 95 mol%
Structural unit derived from (c); 1 to 65 mol%
It is preferable that
Structural unit derived from (a); 5-40 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (c); 5 to 60 mol%
It is more preferable that
When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter, There is a tendency to be excellent in heat resistance and mechanical strength.

Resin [K2] can be produced, for example, in the same manner as the method described as the production method of resin [K1].

In the resin [K3], the proportion of structural units derived from each of the structural units constituting the resin [K3]
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (c); 40 to 98 mol%
It is preferable that
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (c); 50 to 90 mol%
It is more preferable that
Resin [K3] can be produced, for example, in the same manner as described for the production method of resin [K1].

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

Next, the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms which (b) has.
Subsequent to the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b) a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris ( Dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (eg, hydroquinone, etc.) are placed in a flask and reacted, for example, at 60-130 ° C. for 1-10 hours to produce resin [K4]. it can.
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By making it within this range, the storage stability of the colored curable resin composition, the developability when forming the pattern, and the balance of the solvent resistance, heat resistance, mechanical strength and sensitivity of the resulting pattern are improved. Tend. Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used in the resin [K4], and (b1-1) is more preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c).
The reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

Resin [K5] obtains a copolymer of (b) and (c) as a first step in the same manner as in the method for producing resin [K1] described above. Similarly to the above, the obtained copolymer may be used as it is after the reaction, or may be a concentrated or diluted solution, or may be solid (powder) by a method such as reprecipitation. You may use what was taken out as.
The ratio of the structural units derived from (b) and (c) is respectively based on the total number of moles of all the structural units constituting the copolymer.
Structural unit derived from (b); 5 to 95 mol%
Structural unit derived from (c); 5 to 95 mol%
It is preferable that
Structural unit derived from (b); 10 to 90 mol%
Structural unit derived from (c); 10 to 90 mol%
It is more preferable that

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

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

As the resin (B), specifically, 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] Resin such as decyl (meth) acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (Meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3 , 4-epoxytricyclo [5.2.1.0 ^2,6] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3- menu Resin such as ru-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) Acrylic acid copolymer, resin such as benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer [K3]; benzyl (meth) acrylate / (meth) acrylic acid copolymer A resin in which glycidyl (meth) acrylate is added to a resin, a resin in which glycidyl (meth) acrylate is added to a tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / Benzyl (meth) acrylate / (meth) acrylic acid copolymer with glycidyl (meth) acrylate Resin [K4] such as a resin to which a relate is added; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, tricyclodecyl (meth) acrylate / Resin such as a resin obtained by reacting a copolymer of styrene / glycidyl (meth) acrylate with (meth) acrylic acid [K5]; a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate (meth) Examples thereof include a resin [K6] such as a resin obtained by reacting acrylic acid with a resin further reacted with tetrahydrophthalic anhydride.

The resin (B) is preferably a kind selected from the group consisting of a resin [K1], a resin [K2] and a resin [K3], and more preferably from a group consisting of a resin [K2] and a resin [K3]. It is the kind chosen. When these resins are used, the colored curable resin composition is excellent in developability. Resin [K2] is more preferable from the viewpoint of adhesion between the coloring pattern and the substrate.

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, Preferably it is 5,000 to 30,000, and particularly preferably 6,000 to 30,000. When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed area in the developer 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, and more preferably 1.2 to 4.

The acid value of the resin (B) is usually 20 mg-KOH / g to 170 mg-KOH / g, preferably 30 mg-KOH / g to 170 mg-KOH / g, more preferably 40 mg-KOH / g to 170 mg. -KOH / g, more preferably 50 mg-KOH / g to 170 mg-KOH / g. Among them, 50 mg-KOH / g to 150 mg-KOH / g is preferable, 60 mg-KOH / g to 150 mg-KOH / g is more preferable, 60 mg-KOH / g to 135 mg-KOH / g is more preferable, and 70 mg-KOH / g. ˜135 mg-KOH / g is particularly preferred. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (B), and can be determined by titration with an aqueous potassium hydroxide solution, for example.

The content of the resin (B) is preferably 7% by mass to 65% by mass, more preferably 10% by mass to 60% by mass, and further preferably 13% by mass to 60% by mass with respect to the total amount of the solid content. % By mass, particularly preferably 17% by mass to 55% by mass. When the content of the resin (B) is in the above range, a colored pattern can be easily formed, and the resolution and remaining film ratio of the colored pattern tend to be improved.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond. Is a (meth) acrylic acid ester compound.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone. And the above-mentioned (a), (a) and (c).

Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol diester. (Meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more of ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) ) Isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol Hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Is mentioned.
Of these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

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

The content of the polymerizable compound (C) is preferably 1 to 70% by mass, more preferably 2 to 65% by mass, and more preferably 5 to 65% by mass, based on the total amount of the solid content. It is preferably 7 to 65% by mass, more preferably 10 to 60% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass. is there.
The content ratio of the resin (B) and the polymerizable compound (C) [resin (B): polymerizable compound (C)] is preferably 20:80 to 80:20, more preferably on a mass basis. Is from 35:65 to 80:20.
When the content of the polymerizable compound (C) is within the above range, the remaining film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
Examples of the polymerization initiator (D) include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds.

O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one -2-Imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxa) Cyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6 (2-Methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) may be used. Among them, O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1 At least one selected from the group consisting of -one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferred, and N-benzoyloxy -1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred.

Alkylphenone compounds include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one, 2-hydroxy-2-methyl-1-phenylpropane -1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- ( 4-isopropenylphenyl) propan-1-one oligomer, α, α-diethoxyacetophenone, benzyldimethyl ketal, Irgacure 369, 907, 379 (above, manufactured by BASF) and the like.

Biimidazole compounds are 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′. , 5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) ) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxyphenyl) Imidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), an imidazole compound in which the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group ( For example, see JP-A-7-10913. Among these, compounds represented by the following formula and mixtures thereof are preferable.

Examples of triazine compounds include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl)- 1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methyl) Phenyl) etheni ] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Examples include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant (D1) (particularly amines) described later.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and biimidazole compounds, and more preferably Is a polymerization initiator containing an O-acyloxime compound.

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

<Polymerization initiation aid (D1)>
The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator. When the polymerization initiation assistant (D1) is included, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

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

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

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

Carboxylic acid compounds include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

When these polymerization initiation assistants (D1) are used, the content thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). The amount is preferably 1 to 20 parts by mass. When the amount of the polymerization initiation assistant (D1) is within this range, a colored pattern can be formed with higher sensitivity and the productivity of the color filter tends to be improved.

<Solvent (E)>
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, ester solvents (solvents containing —COO— in the molecule and not containing —O—), ether solvents (solvents containing —O— in the molecule and not containing —COO—), ether ester solvents (intramolecular Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O-,- Solvent containing no CO- and -COO-), aromatic hydrocarbon solvent, amide solvent, dimethyl sulfoxide and the like.

Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone, and the like.

Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, die Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl acetate Le 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, dipropylene glycol methyl ether acetate and the like.

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

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.
Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

These solvents may be used alone or in combination of two or more.
Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3- Methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, N-methylpyrrolidone and the like are preferable. Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, di Propylene glycol methyl ether acetate, ethyl lactate, 3-methoxy Chill acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, 4-hydroxy-4-methyl-2-pentanone, N, N- dimethylformamide, N- methylpyrrolidone and the like are more preferable.

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

<Leveling agent (F)>
Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan GK) Can be mentioned.

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

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

The content of the leveling agent (F) is preferably 0.0005% by mass or more and 0.6% by mass or less, more preferably 0.001% by mass or more and 0.000% by mass or more based on the total amount of the colored curable resin composition. 5 mass% or less, more preferably 0.001 mass% or more and 0.2 mass% or less, preferably 0.002 mass% or more and 0.1 mass% or less, more preferably 0.005 mass% or more and 0 or less. 0.07% by mass or less. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>
The colored curable resin composition of the present invention includes additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., if necessary. May be included.

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention includes, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E) used as necessary. It can be prepared by mixing the leveling agent (F), the polymerization initiation assistant (D1) and other components.
The pigment in the case of containing the pigment (P) is preferably mixed with a part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. . Under the present circumstances, you may mix | blend a pigment dispersant and some or all of resin (B) as needed. As the pigment dispersant, commercially available surfactants can be used, and silicone, fluorine, ester, cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, and other surface activities. Agents and the like. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. , KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solpers (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF Japan K.K.), Ajisper (registered trademark) (Manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (manufactured by Big Chemie Co., Ltd.) and the like, and these can be used alone or in combination of two or more. The desired colored curable resin composition can be prepared by mixing the remaining components in the pigment dispersion thus obtained so as to have a predetermined concentration.
It is preferable to prepare a solution by dissolving the compound (Z) in part or all of the solvent (E) in advance. The solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.
The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.

<Color filter manufacturing method>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Of these, the photolithographic method is preferable. The photolithographic method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithography method, a colored coating film that is a cured product of the colored composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and the colored coating film thus formed are the color filter of the present invention.
The film thickness of the color filter to be produced is not particularly limited, and can be appropriately adjusted according to the purpose and application, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5. ~ 6 μm.

As the substrate, quartz glass, borosilicate glass, alumina silicate glass, glass plate such as soda lime glass coated with silica on the surface, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the substrate In addition, aluminum, silver, or a silver / copper / palladium alloy thin film is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

Formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be produced as follows.
First, a colored curable resin composition is applied on a substrate, dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth colored composition layer is obtained.
Examples of the coating method include spin coating, slit coating, and slit and spin coating.
The temperature for heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
When drying under reduced pressure, it is preferably performed at a temperature of 20 to 25 ° C. under a pressure of 50 to 150 Pa.
The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specific examples include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.
Use an exposure device such as a mask aligner or a stepper because the entire exposure surface can be illuminated with parallel rays uniformly, or the photomask can be accurately aligned with the substrate on which the colored composition layer is formed. Is preferred.

A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed.
As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass, and even more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.

Furthermore, it is preferable to post-bake the obtained colored pattern. The post bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-bake time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

This application claims the benefit of priority based on Japanese Patent Application No. 2014-186017 filed on September 12, 2014. The entire contents of Japanese Patent Application No. 2014-186017 filed on September 12, 2014 are incorporated herein by reference.

Next, the present invention will be described more specifically with reference to examples.
In Examples and Comparative Examples, “%” and “part” representing content or use amount are based on mass unless otherwise specified.
The structure of the compound was confirmed by mass spectrometry (LC; Agilent 1200 model, MASS; Agilent LC / MSD6130 model).

Example 1
3-amino-4-hydroxybenzoic acid (Tokyo Chemical Industry Co., Ltd.) 10 parts, 4- (diethylamino) salicylaldehyde (Tokyo Chemical Industry Co., Ltd.) 12.8 parts, benzoic acid (Tokyo Chemical Industry Co., Ltd.) 2.73 parts), 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 157 parts and ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 7.43 parts are mixed and stirred at 120 ° C. for 3 hours. To obtain a mixture (1).
7.46 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.79 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 49.8 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) And 12.7 parts of 4- (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred at 120 ° C. for 14 hours to obtain a mixture (2).
The obtained mixture (1) and mixture (2) were mixed, and further 3.76 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.41 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) Then, 52.5 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 6.35 parts of 4- (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred at 120 ° C. for 8 hours. The reaction solution was cooled to room temperature, and the precipitated crystals were obtained as a residue of suction filtration. To this residue was added 140 parts of tetrahydrofuran, and the mixture was stirred at 70 ° C. for 1 hour, and insoluble matter was obtained as a residue of suction filter. To this residue was added 120 parts of tetrahydrofuran, and the mixture was stirred at 70 ° C. for 1 hour, and insoluble matter was obtained as a residue of a suction filter. To this residue, 340 parts of N, N-dimethylformamide was added, dissolved by heating to 90 ° C., and then allowed to stand at 0 ° C. to 5 ° C. The precipitated crystals were obtained as a suction filtration residue. This residue was dried under reduced pressure at 60 ° C. to obtain 5.69 parts of a compound represented by the formula (Ad1-1).

Next, 3.8 parts of the compound represented by the formula (Ad1-1) and 1.4 parts of 2- (trimethylsilyl) ethanol were added to 100 parts of dehydrated chloroform. To the obtained mixture, 2.3 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and 1.5 parts of 4-dimethylaminopyridine were further added and stirred at 30 ° C. for 6 hours. Water was added to the obtained reaction mixture, the organic layer was extracted, chloroform was distilled off, and a yellow solid was obtained. The mixture was dried at 60 ° C. under reduced pressure for 24 hours to obtain 4.2 parts of a compound represented by the formula (Z-1).

Identification of compound represented by formula (Z-1) (mass spectrometry) ionization mode = ESI +: m / z = 479.2 [M + 1] ⁺
Exact Mass: 478.2

Example 2
Example 1 was synthesized in the same manner as in Example 1 except that a compound represented by the following formula (d-1) was used instead of 3-amino-4-hydroxybenzoic acid, and the compound represented by formula (Ad1-2) The compound represented was obtained.

Next, 3.6 parts of the compound represented by the formula (Ad1-2) and 2.0 parts of triethylamine are added to 300 parts of chloroform, 3.1 parts of methacrylic anhydride is further added, and the mixture is kept at 50 ° C. for 3 hours. did. To the obtained mixture, 300 parts of water was added, the organic layer was extracted, chloroform was distilled off, and a yellow solid was obtained. It was dried at 60 ° C. under reduced pressure for 24 hours to obtain 3.8 parts of a compound represented by the formula (Z-41).

Identification of compound represented by formula (Z-41) (mass spectrometry) ionization mode = ESI +: m / z = 419.4 [M + 1] ⁺
Exact Mass: 418.4

Synthesis example 1
An appropriate amount of nitrogen was passed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to make a nitrogen atmosphere, 100 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85 ° C. with stirring. Then, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2. 1.0 ^2,6 ] decan-9-yl acrylate mixture (content ratio is 50:50 in molar ratio) 171 parts dissolved in propylene glycol monomethyl ether acetate 40 parts using a dropping pump over about 5 hours And dripped. On the other hand, a solution obtained by dissolving 26 parts of polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate was placed in the flask over another 5 hours using another dropping pump. It was dripped. After completion of dropping of the polymerization initiator, the temperature was maintained at the same temperature for about 3 hours, and then cooled to room temperature to obtain a copolymer (resin B1) solution having a solid content of 43.5%. The obtained resin B1 had a weight average molecular weight of 8,000, a molecular weight distribution of 1.98, and an acid value in terms of solid content of 53 mgKOH / g.

(Preparation of colored curable resin composition)
Example 3
Colorant (A): C.I. I. Pigment Green 58 (pigment) 27 parts;
12 parts acrylic pigment dispersant;
Resin (B): Resin B1 (solid content conversion) 9.5 parts; and Solvent (E): Propylene glycol monomethyl ether acetate 180 parts;
And a pigment dispersion (3) in which the pigment was sufficiently dispersed using a bead mill was obtained.

Colorant (A): 2.0 parts of the compound represented by formula (Z-1);
Resin (B): Resin B1 (solid content conversion) 40 parts;
Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 49 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound)
9.8 parts;
Solvent (E): 670 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.15 parts; and Pigment dispersion (3) 228.5 parts;
Were mixed to obtain a colored curable resin composition (J1).

Example 4
C. of the colorant (A) I. Pigment Green 58 (pigment) is changed to C.I. I. A colored curable resin composition (J2) was obtained in the same manner as in Example 3 except that the pigment green 36 (pigment) was used instead.

Example 5
In the same manner as in Example 3 except that the compound represented by the formula (Z-1) of the colorant (A) is replaced with the compound represented by the formula (Z-41), a colored curable resin composition (J3 )

Example 6
C. of the colorant (A) I. Pigment Green 58 (pigment) is changed to C.I. I. A colored curable resin composition (J4) was obtained in the same manner as in Example 5 except that it was replaced with CI Pigment Green 36 (pigment).

Comparative Example 1
Colorant (A): C.I. I. Pigment Green 58 (pigment) 27 parts;
12 parts acrylic pigment dispersant;
Resin (B): Resin B1 (solid content conversion) 9.5 parts; and Solvent (E): Propylene glycol monomethyl ether acetate 180 parts;
And a pigment dispersion (5) in which the pigment was sufficiently dispersed using a bead mill was obtained.

Colorant (A): 1.0 part of a compound represented by formula (d0);
Resin (B): Resin B1 (solid content conversion) 40 parts;
Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 49 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound)
9.8 parts;
Solvent (E): 670 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.15 parts; and pigment dispersion (5) 228.5 parts;
Were mixed to obtain a colored curable resin composition (J5).

[Film thickness measurement]
The film thickness was measured using DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.

[Preparation of resin composition for sublimation test (SJS)]
Resin: Methacrylic acid / benzyl methacrylate (molar ratio: 30/70) copolymer (manufactured by Taoka Chemical Co., Ltd., average molecular weight 10700, acid value 70 mg KOH / g) 33.8% propylene glycol monomethyl ether acetate solution 40.2 Part;
Polymerizable compound: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 5.8 parts;
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF Japan Ltd.) 0.58 parts;
Leveling agent: polyether-modified silicone (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.01 part;
Solvent: 46.6 parts propylene glycol monomethyl ether;
Solvent: 6.8 parts propylene glycol monomethyl ether acetate;
Were mixed to obtain a resin composition for sublimation test (SJS).

[Formation of resin coating film for sublimation test (SJSM)]
On a 2-inch square glass substrate (Eagle XG; manufactured by Corning), the resin composition for sublimation test (SJS) obtained above was applied by spin coating, and volatile components were volatilized at 100 ° C. for 3 minutes. . After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.), light irradiation was performed with an exposure dose of 150 mJ / cm ² (based on 365 nm) in an air atmosphere. A resin coating film for sublimation test (SJSM) (thickness: 2.2 μm) was formed by heating at 220 ° C. for 2 hours in an oven.

Example 7
[Preparation of colored pattern and evaluation of sublimation]
The colored curable resin composition (J1) obtained in Example 3 was applied on a 2-inch square glass substrate (Eagle XG; manufactured by Corning) by spin coating, and then prebaked at 100 ° C. for 3 minutes for coloring. A composition layer was formed. After cooling, the distance between the substrate on which the colored composition layer is formed and the photomask made of quartz glass is set to 200 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Corporation) is used, and 80 mJ / cm ^{2 in the} atmosphere. The exposure amount (standard on 365 nm) was used. A photomask having a 100 μm line and space pattern was used. The colored composition layer after the exposure was developed by being immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C. for 70 seconds, and washed with water. The film thickness was measured. The results are shown in Table 1.
The colored coating film and the resin coating film for sublimation test (SJSM) obtained above were opposed to each other with an interval of 70 μm, and a post-baking was performed at 230 ° C. for 10 minutes to obtain a colored pattern. . The color difference (ΔEab *) before and after heating of the resin coating film for sublimation test (SJSM) was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). The color difference (ΔEab *) was 4.0. A color difference (ΔEab *) of 5.0 or more indicates that the colorant has sublimability. The results are shown in Table 1. In Table 1, “◯” indicates that the colorant does not have sublimability, and “x” indicates that the colorant has sublimability.

Examples 8 to 10 and Comparative Example 2
Except for replacing the colored curable resin composition (J1) obtained in Example 3 with the colored curable resin composition (J2) to the colored curable resin composition (J5), respectively, Example 7 and Similarly, a colored pattern was obtained and evaluated for sublimation. The results are shown in Table 1.

When forming a color filter from a colored curable resin composition containing the compound of the present invention, sublimation of the colorant can be suppressed. The color filter using the colored curable resin composition containing the compound of the present invention is suitably used for a display device such as a liquid crystal display device.

Claims (11)

A compound represented by formula (Z).

[In Formula (Z), R ¹ and R ² each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a group containing an acryloyl group, or a group containing a methacryloyl group. Or represents a group containing a silicon atom.
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, a nitro group, or a carbon number of 1 to 20 An alkyl group having 1 to 20 carbon atoms, a group containing an acryloyl group, a group containing a methacryloyl group, or a group containing a silicon atom.
Provided that at least ^one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is a group containing an acryloyl group, a group containing a methacryloyl group, or It is a group containing a silicon atom. ] The compound according to claim 1, wherein the group containing a silicon atom is a group represented by the formula (Z1).

[Wherein R ^11A represents a single bond or an alkanediyl group having 1 to 10 carbon atoms, and —CH ₂ — contained in the alkanediyl group represents —O—, —CO—, —NR ¹⁰ —, — OCO—, —COO—, —OCONH—, —CONH— or —NHCO— may be substituted, and the hydrogen atom contained in the alkanediyl group may have a hydroxyl group of 1 to 4 carbon atoms. The alkyl group may be substituted.
R ¹⁰ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
R ^12A , R ^13A and R ^14A each independently represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
* Represents a bond with a nitrogen atom or a carbon atom. ] The compound according to claim 1 or 2, wherein the group containing an acryloyl group or the group containing a methacryloyl group is a group represented by the formula (Z2).

[Wherein R ^15A represents an alkanediyl group having 1 to 10 carbon atoms, and —CH ₂ — contained in the alkanediyl group represents —O—, —CO—, —NR ¹¹ —, —OCO—, The hydrogen atom contained in the alkanediyl group may be substituted with —COO—, —OCONH—, —CONH— or —NHCO—, and the alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group May be substituted.
R ¹¹ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
R ^16A represents an acryloyl group or a methacryloyl group.
* Represents a bond with a nitrogen atom or a carbon atom. ] A colorant comprising the compound according to any one of claims 1 to 3. The colorant according to claim 4, further comprising a green pigment. The colorant according to claim 5, wherein the green pigment is at least one selected from the group consisting of a halogenated copper phthalocyanine pigment and a halogenated zinc phthalocyanine pigment. The colorant according to claim 5 or 6, wherein the green pigment is at least one selected from the group consisting of a chlorinated copper phthalocyanine pigment, a brominated copper phthalocyanine pigment, and a brominated zinc phthalocyanine pigment. Green pigment is C.I. I. Pigment green 36 and C.I. I. The colorant according to any one of claims 5 to 7, which is at least one selected from the group consisting of CI Pigment Green 58. A colored curable resin composition comprising the colorant, resin, polymerizable compound and polymerization initiator according to any one of claims 4 to 8. A color filter formed from the colored curable resin composition according to claim 9. A liquid crystal display device comprising the color filter according to claim 10.