JP2022115798A - Coloring curable resin composition - Google Patents

Abstract

To provide a coloring curable resin composition useful for producing a color filter making contrast excellent.SOLUTION: A coloring curable resin composition that contains a coloring agent (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D) is such that: the coloring agent (A) contains a squarylium dye; an average ethylenic unsaturated group equivalent number of the polymerizable compound (C), represented by formula (1) is less than 96.0; and a content of the squarylium dye is 3-140 pts.mass based on 100 pts.mass of the polymerization initiator (D).SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a colored curable resin composition, a color filter, a display device and a solid-state imaging device.

Color filters used in display devices such as liquid crystal display devices, electroluminescence display devices and plasma displays and solid-state imaging devices such as CCD and CMOS sensors are produced from colored curable resin compositions. As the polymerizable compound used in the colored curable resin composition, dipentaerythritol hexaacrylate is mainly used in Examples of Patent Documents 1 and 2.

JP 2020-055956 A JP 2019-163233 A

However, a color filter formed from a colored curable resin composition containing dipentaerythritol hexaacrylate sometimes has insufficient contrast.

An object of the present invention is to provide a colored curable resin composition useful for producing a color filter with good contrast.

［式（Ｉ）中、
Ｒ¹～Ｒ⁸は、それぞれ独立に、水素原子、ハロゲン原子、ヒドロキシ基、置換基を有していてもよい炭素数１～２０の飽和炭化水素基、又は置換基を有していてもよい炭素数１～２０のアルコキシ基を表す。
Ｒ⁹及びＲ¹⁰は、それぞれ独立に、置換基を有していてもよい炭素数１～２０の２価の脂肪族炭化水素基を表し、該脂肪族炭化水素基に含まれるメチレン基は－Ｏ－に置き換わっていてもよい。
Ｒ¹¹及びＲ¹²は、それぞれ独立に、芳香族炭化水素環を有する炭素数６～２０の炭化水素基を表し、該炭化水素基は置換基を有していてもよく、該炭化水素基に含まれるメチレン基は－Ｏ－に置き換わっていてもよい。
Ｒ¹³は、水素原子又は炭素数１～８の飽和炭化水素基を表す。］

［式（ＩＩＩ）中、
Ｒ³¹～Ｒ³⁸は、それぞれ独立に、水素原子、ヒドロキシ基、置換基を有していてもよい炭素数１～２０のアルキル基、又は置換基を有していてもよい炭素数１～２０のアルコキシ基を表す。
Ｒ³⁹～Ｒ⁴²は、それぞれ独立に、置換基を有していてもよい炭素数１～２０の炭化水素基を表し、Ｒ³⁹～Ｒ⁴²のうち少なくとも一つは、カルボキシ基を置換基として有する炭素数１～２０の脂肪族炭化水素基であり、かつ、Ｒ³⁹～Ｒ⁴²のうち少なくとも一つは、置換基を有していてもよい炭素数６～２０の芳香族炭化水素基であり、該脂肪族炭化水素基に含まれるメチレン基は－Ｏ－に置き換わっていてもよい。］
［３］ 前記平均エチレン性不飽和基当量数が８３．０以上である［１］または［２］に記載の着色硬化性樹脂組成物。
［４］ 前記重合性化合物（Ｃ）は、エチレン性不飽和結合を３つ以上５つ以下有する重合性化合物を含む［１］～［３］のいずれか１項に記載の着色硬化性樹脂組成物。
［５］ 前記重合性化合物（Ｃ）は、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート及びグリセリントリ（メタ）アクリレートから選択される少なくとも１種を含む［１］～［４］のいずれか１項に記載の着色硬化性樹脂組成物。
［６］ 前記重合開始剤（Ｄ）がＯ－アシルオキシム化合物を含む［１］～［５］のいずれか１項に記載の着色硬化性樹脂組成物。
［７］ ［１］～［６］のいずれか１項に記載の着色硬化性樹脂組成物から形成されるカラーフィルタ。
［８］ ［７］に記載のカラーフィルタを含む表示装置。
［９］ ［７］に記載のカラーフィルタを含む固体撮像素子。 That is, the gist of the present invention is as follows.
[1] Colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D),
The coloring agent (A) contains a squarylium dye,
The average ethylenically unsaturated group equivalent number represented by the formula (1) of the polymerizable compound (C) is less than 96.0,
The content of the squarylium dye is 3 to 140 parts by mass with respect to 100 parts by mass of the polymerization initiator (D).
<Average ethylenically unsaturated group equivalent number>
Average number of ethylenically unsaturated group equivalents of the polymerizable compound (C) = _{ΣK i} mi (1)
[In formula (1),
K _i : A value represented by (molecular weight/number of ethylenically unsaturated bonds) of component i among all polymerizable compounds (C) contained in the colored curable resin composition.
m _i : represents the mole fraction of the i component. ]
[2] The colored curable resin composition according to [1], wherein the squarylium dye contains at least one selected from the group consisting of the compound represented by formula (I) and the compound represented by formula (III). .

[in the formula (I),
R ¹ to R ⁸ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, or optionally having a substituent It represents an alkoxy group having 1 to 20 carbon atoms.
R ⁹ and R ¹⁰ each independently represent an optionally substituted divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and the methylene group contained in the aliphatic hydrocarbon group is - O- may be substituted.
R ¹¹ and R ¹² each independently represent a hydrocarbon group having 6 to 20 carbon atoms and having an aromatic hydrocarbon ring, and the hydrocarbon group may have a substituent. The methylene group contained may be replaced with -O-.
R ¹³ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms. ]

[In the formula (III),
R ³¹ to R ³⁸ each independently represent a hydrogen atom, a hydroxy group, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted C 1 to 20 represents an alkoxy group.
R ³⁹ to R ⁴² each independently represent an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ³⁹ to R ⁴² has a carboxy group as a substituent; and at least one of R ³⁹ to R ⁴² is an optionally substituted aromatic hydrocarbon group with 6 to 20 carbon atoms. and the methylene group contained in the aliphatic hydrocarbon group may be replaced with -O-. ]
[3] The colored curable resin composition according to [1] or [2], wherein the average number of ethylenically unsaturated group equivalents is 83.0 or more.
[4] The colored curable resin composition according to any one of [1] to [3], wherein the polymerizable compound (C) contains a polymerizable compound having 3 or more and 5 or less ethylenically unsaturated bonds. thing.
[5] The polymerizable compound (C) contains at least one selected from pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate and glycerin tri(meth)acrylate [1] to [4] Colored curable resin composition according to any one of.
[6] The colored curable resin composition according to any one of [1] to [5], wherein the polymerization initiator (D) contains an O-acyloxime compound.
[7] A color filter formed from the colored curable resin composition according to any one of [1] to [6].
[8] A display device including the color filter of [7].
[9] A solid-state imaging device including the color filter according to [7].

ADVANTAGE OF THE INVENTION According to this invention, it is possible to provide a colored curable resin composition useful for producing a color filter with good contrast.

The colored curable resin composition of the present invention includes a coloring agent (hereinafter sometimes referred to as a coloring agent (A)), a resin (hereinafter sometimes referred to as a resin (B)), a polymerizable compound (hereinafter, a polymerizable compound (C)) and a polymerization initiator (hereinafter sometimes referred to as a polymerization initiator (D)).
Colorant (A) comprises a squarylium dye.
The colored curable resin composition of the present invention may contain a solvent (hereinafter sometimes referred to as solvent (E)).
The colored curable resin composition of the present invention may contain a leveling agent (hereinafter sometimes referred to as leveling agent (F)).
In this specification, the compounds exemplified as each component can be used singly or in combination unless otherwise specified.

<Colorant (A)>
Colorant (A) comprises a squarylium dye. The squarylium dye is not particularly limited, and known dyes can be used.

The squarylium dye preferably contains a compound represented by formula (I) (hereinafter sometimes referred to as compound (I)). The compound (I) includes the resonance structure of formula (I), and each group in formula (I) or its resonance structure is formed around the bond axis of a carbon-carbon single bond or a carbon-nitrogen single bond. Compounds obtained by rotation are also intended to be included.

[in the formula (I),
R ¹ to R ⁸ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, or optionally having a substituent It represents an alkoxy group having 1 to 20 carbon atoms.
R ⁹ and R ¹⁰ each independently represent a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and the methylene group contained in the aliphatic hydrocarbon group is - O- may be substituted.
R ¹¹ and R ¹² each independently represent a hydrocarbon group having 6 to 20 carbon atoms and having an aromatic hydrocarbon ring, and the hydrocarbon group may have a substituent. The methylene group contained may be replaced with -O-.
R ¹³ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms. ]

Halogen atoms represented by R ¹ to R ⁸ include fluorine, chlorine, bromine and iodine atoms.

The saturated hydrocarbon groups having 1 to 20 carbon atoms represented by R ¹ to R ⁸ may be linear, branched or cyclic. Specific examples of linear or branched saturated hydrocarbon groups include methyl group, ethyl group, propyl group, isobutyl group, butyl group, tert-butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, heptadecyl group, undecyl group and the like. Cyclic saturated hydrocarbon groups include cyclopropyl, 1-methylcyclopropyl, cyclopentyl, cyclohexyl, 1,2-dimethylcyclohexyl, cyclooctyl, 2,4,6-trimethylcyclohexyl, 4- A cyclohexylcyclohexyl group and the like can be mentioned.
Substituents of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ to R ⁸ include halogen atoms such as fluorine, ^chlorine , ^bromine and iodine atoms; hydroxy group; R ^a and R ^b are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; an alkoxycarbonyl group having 1 to 10 carbon atoms such as a carbonyl group; and the like.

Examples of the alkoxy groups having 1 to 20 carbon atoms represented by R ¹ to R ⁸ include groups in which —O— is bonded to the bond of the above saturated hydrocarbon groups having 1 to 20 carbon atoms. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group , 2-ethylhexyloxy group and the like.
Substituents for the alkoxy group having 1 to 20 carbon atoms represented by R ¹ to R ⁸ include halogen atoms such as fluorine, chlorine, bromine and iodine atoms; hydroxy; —NR ^c R ^d (R ^c and R ^d are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; a methoxycarbonyl group and an ethoxycarbonyl group An alkoxycarbonyl group in which the alkoxy moiety has 1 to 10 carbon atoms, such as
The saturated hydrocarbon group represented by R ¹ to R ⁸ preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 7 carbon atoms, and still more preferably 1 to 4 carbon atoms.
The saturated hydrocarbon groups represented by R ¹ to R ⁸ are preferably linear or branched saturated hydrocarbon groups, more preferably linear saturated hydrocarbon groups.

Among R ¹ to R ⁸ , R ¹ to R ⁴ are preferably hydrogen atoms or methyl groups, more preferably hydrogen atoms. Further, when R ¹ to R ⁴ are hydrogen atoms or methyl groups, more preferably when R ¹ to R ⁴ are hydrogen atoms, R ⁵ to R ⁸ are each independently a hydrogen atom, a hydroxy group, or a substituent It is preferably a saturated hydrocarbon group having 1 to 20 carbon atoms which may have or an alkoxy group having 1 to 20 carbon atoms which may have a substituent, and is a hydrogen atom or a hydroxy group is more preferred.

Two to four of R ¹ to R ⁸ (preferably R ⁵ to R ⁸ ) are preferably independently hydroxy groups, and R ¹ to R ⁸ (preferably R ⁵ to R ⁸ ) More preferably, two to three of them are each independently hydroxy groups, and two of R ¹ to R ⁸ (preferably R ⁵ to R ⁸ ) are each independently hydroxy groups. is more preferred.

The divalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms represented by R ⁹ and R ¹⁰ may be either saturated or unsaturated, preferably saturated. The divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear, branched or cyclic, preferably linear or branched.

Examples of divalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms include methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, Hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11 -diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane -Divalent linear aliphatic hydrocarbon groups such as 1,17-diyl group and propenylene group; ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group , propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 2,2-dimethylpropane- divalent branched chain aliphatic hydrocarbon groups such as 1,3-diyl group, pentane-1,4-diyl group and 2-methylbutane-1,4-diyl group;
A cyclic divalent aliphatic hydrocarbon group may be monocyclic or polycyclic. The cyclic divalent aliphatic hydrocarbon group includes a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, and a cyclooctane-1,5-diyl group. monocyclic divalent aliphatic hydrocarbon groups such as groups; norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl and polycyclic divalent aliphatic hydrocarbon groups such as groups.
The number of carbon atoms in the divalent aliphatic hydrocarbon group represented by R ⁹ and R ¹⁰ is preferably 1-10, more preferably 1-7, still more preferably 1-4.
The divalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms represented by R ⁹ and R ¹⁰ are preferably saturated linear or branched aliphatic hydrocarbon groups, and saturated linear A triangular aliphatic hydrocarbon group is more preferred.
The divalent aliphatic hydrocarbon groups represented by R ⁹ and R ¹⁰ may be the same or different, but are preferably the same.

The methylene group contained in the divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be replaced with -O-. Examples of the group in which the methylene group contained in the divalent aliphatic hydrocarbon group is replaced with -O- include groups represented by the following formulae. In the following formula, * on the left represents a bond with a nitrogen atom, and * on the right represents a bond with an oxygen atom.

The divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ⁹ and R ¹⁰ may have a substituent, and the substituent may be fluorine atom, chlorine atom, bromine atom, iodine atom, halogen atoms such as atoms; hydroxy group; —NR ^e R ^f (R ^e and R ^f are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); nitro group; methoxycarbonyl group, ethoxycarbonyl an alkoxycarbonyl group having 1 to 10 carbon atoms such as a group;
Among them, the divalent aliphatic hydrocarbon groups represented by R ⁹ and R ¹⁰ are preferably methylene group, ethylene group, propane-1,3-diyl group and butane-1,4-diyl group.

The hydrocarbon group having 6 to 20 carbon atoms and having an aromatic hydrocarbon ring represented by R ¹¹ and R ¹² includes a group having a bond on the aromatic hydrocarbon ring (hereinafter referred to as an aromatic hydrocarbon group), Examples thereof include aralkyl groups having 7 to 20 carbon atoms. These may have a substituent.
Examples of the aromatic hydrocarbon ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring and the like, preferably benzene ring.
Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, phenanthryl group, tolyl group, xylyl group, dimethylethylphenyl group, dimethylpropylphenyl group, dimethylbutylphenyl group, trimethylphenyl group, diisopropylphenyl and the like. Among them, aromatic hydrocarbon groups having an alkyl group at the ortho position are preferred, such as 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl and 2,6-dimethylphenyl. -4-ethyl-phenyl group, 2,6-dimethyl-4-propyl-phenyl group, 2,6-dimethyl-4-butyl-phenyl group and the like. Further, when the alkyl group at the ortho position is bulky, the light resistance tends to be excellent.
When the aromatic hydrocarbon group has a substituent, it may have one or more substituents. When the aromatic hydrocarbon group has multiple substituents, each substituent may be the same or different. Examples of the substituent include a hydroxy group; a carboxy group; a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom and a bromine atom; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; a sulfamoyl group; alkylsulfonyl groups having 1 to 6 carbon atoms such as; alkoxycarbonyl groups having 1 to 6 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group;
The hydrocarbon group having 6 to 20 carbon atoms and having an aromatic hydrocarbon ring may have a substituent such as a hydroxy group, a carboxy group, a halogen atom or an alkoxy group, and preferably has a hydroxy group.

When the aromatic hydrocarbon group optionally having substituents has a methylene group, the methylene group may be replaced with -O-.

The aralkyl group having 7 to 20 carbon atoms is a group in which an alkanediyl group having 1 to 5 carbon atoms such as a methylene group, ethylene group, propylene group, etc. is bonded to the aromatic hydrocarbon ring described in the above aromatic hydrocarbon group. are mentioned. The aralkyl group includes benzyl group, phenylethyl group, naphthylmethyl group, naphthylethyl group and the like.
The aralkyl group having 7 to 20 carbon atoms may have a substituent, and when there are a plurality of substituents, each substituent may be the same or different. The substituent may be bonded to the aromatic hydrocarbon ring or the alkanediyl group, and the substituent capable of bonding to the aromatic hydrocarbon ring is a substituent of the aromatic hydrocarbon group It is the same as the explained groups.

When the optionally substituted aralkyl group having 7 to 20 carbon atoms has a methylene group, the methylene group may be replaced with -O-.

The aromatic hydrocarbon ring-containing hydrocarbon groups of 6 to 20 carbon atoms represented by R ¹¹ and R ¹² may be the same or different, but are preferably the same.
Among them, the hydrocarbon group having 6 to 20 carbon atoms having an aromatic hydrocarbon ring represented by R ¹¹ and R ¹² is preferably dimethylethylphenyl group, dimethylpropylphenyl group, dimethylbutylphenyl group, dimethylmethoxyphenyl group. , dimethylethoxyphenyl group, dimethylpropoxyphenyl group, more preferably 2,6-dimethyl-4-ethyl-phenyl group, 2,6-dimethyl-4-propyl-phenyl group, 2,6-dimethyl-4-butyl- phenyl group, 2,6-dimethyl-4-methoxy-phenyl group, 2,6-dimethyl-4-ethoxy-phenyl group, 2,6-dimethyl-4-propoxy-phenyl group, more preferably 2,6-dimethyl -4-methoxy-phenyl group, 2,6-dimethyl-4-ethoxy-phenyl group, 2,6-dimethyl-4-propoxy-phenyl group, even more preferably 2,6-dimethyl-4-ethoxy-phenyl group is. Moreover, it is preferable to have a hydroxy group as a substituent of an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group and a propoxy group.

The saturated hydrocarbon group having 1 to 8 carbon atoms represented by R ¹³ may be linear, branched or cyclic. Specific examples of linear or branched saturated hydrocarbon groups include methyl group, ethyl group, propyl group, isobutyl group, butyl group, tert-butyl group, hexyl group, heptyl group and octyl group. mentioned. Cyclic saturated hydrocarbon groups include cyclopropyl, 1-methylcyclopropyl, cyclopentyl, cyclohexyl, 1,2-dimethylcyclohexyl and cyclooctyl groups.
Among them, R ¹³ is particularly preferably a hydrogen atom.

Examples of compound (I) include compounds represented by formulas (I-1) to (I-240) shown in Tables 1 to 3, and the like.

In Tables 1 to 3, A1-1 to A1-4 represent groups represented by the following formulae. In the following formula, * on the left represents a bond with a nitrogen atom, and * on the right represents a bond with an oxygen atom.

In Tables 1 to 3, A2-1 to A2-5 represent groups represented by the following formulae. In the following formula, * represents a bond.

Further, as the compound (I), in addition to the compounds represented by the above formulas (I-1) to (I-240), compounds represented by the following formula (II) (hereinafter referred to as compound (II) There is), and compound (II) is preferred. Compound (II) has good light resistance.

[in the formula (II),
R ¹ to R ¹⁰ have the same meanings as in formula (I).
X ¹ and X ² each independently represent a hydrocarbon group having 1 to 14 carbon atoms having at least one group selected from the group consisting of a hydroxy group and a carboxy group, a hydroxy group and a carboxy group; The methylene group contained in may be replaced with -O-.
R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 13 carbon atoms.
n1 and n2 each independently represent an integer of 1 to 5;
However, the total number of carbon atoms of (X ¹ ) _n1 and (R ¹⁴ ) _5-n1 and the total number of carbon atoms of (X ² ) _n2 and (R ¹⁵ ) _5-n2 are each 14 or less. ]

The hydrocarbon groups having 1 to 14 carbon atoms represented by X ¹ and X ² include aliphatic hydrocarbon groups, aromatic hydrocarbon groups and groups combining these.
Linear aliphatic hydrocarbon groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group. be done.
Branched aliphatic hydrocarbon groups include isopropyl group, sec-butyl group, tert-butyl group, methylpentyl group, ethylpentyl group, methylhexyl group, ethylhexyl group, propylhexyl group, tert-octyl group and the like. and preferably isopropyl group, sec-butyl group, tert-butyl group and ethylhexyl group.
Cyclic aliphatic hydrocarbon groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, and adamantyl groups.
Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl, 2,6- diethylphenyl group, 2-methyl-6-ethylphenyl group and the like.
Groups in which these groups are combined include an alkylcycloalkyl group, a cycloalkylalkyl group, an aralkyl group, and the like.
The number of carbon atoms in the hydrocarbon group having 1 to 14 carbon atoms represented by X ¹ and X ² is preferably 1 to 10, more preferably 1 to 7, even more preferably 1 to 4.
The hydrocarbon group having 1 to 14 carbon atoms represented by X ¹ and X ² is preferably a linear or branched aliphatic hydrocarbon group, more preferably a linear aliphatic hydrocarbon group and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group.
The hydrocarbon groups having 1 to 14 carbon atoms represented by X ¹ and X ² may be the same or different, but are preferably the same.
X ¹ and X ² are each independently preferably a hydrocarbon group having 1 to 10 carbon atoms and having at least one group selected from the group consisting of a hydroxy group and a carboxy group,
X ¹ and X ² are each independently more preferably a hydrocarbon group having 1 to 7 carbon atoms and having at least one group selected from the group consisting of a hydroxy group and a carboxy group,
X ¹ and X ² are each independently more preferably a hydrocarbon group having 1 to 4 carbon atoms and having at least one group selected from the group consisting of a hydroxy group and a carboxy group,
X ¹ and X ² are each independently more preferably a hydrocarbon group having 1 to 4 carbon atoms and having a hydroxy group.

A methylene group contained in the hydrocarbon group having 1 to 14 carbon atoms may be replaced with -O-.

Examples of the hydrocarbon group having 1 to 13 carbon atoms represented by R ¹⁴ and R ¹⁵ include the same groups as those explained as the hydrocarbon group having 1 to 14 carbon atoms represented by X ¹ and X ² above. be done.
R ¹⁴ and R ¹⁵ may be the same or different, but are preferably the same.
Among them, R ¹⁴ and R ¹⁵ are particularly preferably hydrogen atoms.

n1 and n2 each independently represent an integer of 1 to 5, more preferably 1 to 2, even more preferably 1;

The total carbon number of (X ¹ ) _n1 and (R ¹⁴ ) _5-n1 and the total carbon number of (X ² ) _n2 and (R ¹⁵ ) _5-n2 are each 14 or less. When there are multiple X ¹ , X ² , R ¹⁴ and R ¹⁵ , each X ¹ , X ² , R ¹⁴ and R ¹⁵ may be the same or different.

Compound (II) includes compounds represented by the following formula (II-a), specifically represented by formulas (II-1) to (II-540) shown in Tables 4 to 12. and the like.

In Tables 4 to 12, A1-1 to A1-4 represent the same groups as above.

In Tables 4 to 12, A3-1 to A3-3 represent groups represented by the following formulas. In the following formula, * represents a bond.

In Tables 4 to 12, A4-1 to A4-3 represent groups represented by the following formulae. In the following formula, * represents a bond.

The compounds represented by formulas (I), (II) and (II-a) each preferably have 2 to 10, more preferably 3 to 9 and even more preferably 4 to 8 hydroxy groups.

As compound (I),
Compounds represented by formulas (I-1) to (I-180), formulas (II-121) to (II-180), and formulas (II-331) to (II-375) are preferred,
Formula (I-25) ~ Formula (I-36), Formula (I-85) ~ Formula (I-96), Formula (I-145) ~ Formula (I-156), Formula (I-169) ~ Formula Compounds represented by (I-181), formulas (II-121) to (II-150), and formulas (II-361) to (II-375) are more preferred,
Compounds represented by formulas (II-133) to (II-135) are more preferred, and compounds represented by formula (II-135) are particularly preferred.

The compound represented by formula (I) can be synthesized, for example, by the method described in JP-A-2020-055956.

The squarylium dye preferably contains a compound represented by formula (III) (hereinafter sometimes referred to as compound (III)). Note that compound (III) includes the resonance structure of formula (III), and each group in formula (III) or its resonance structural formula is formed around the bond axis of a carbon-carbon single bond or a carbon-nitrogen single bond. Compounds obtained by rotation are also intended to be included.

[in the formula (III),
R ³¹ to R ³⁸ each independently represent a hydrogen atom, a hydroxy group, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted C 1 to 20 represents an alkoxy group.
R ³⁹ to R ⁴² each independently represent an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ³⁹ to R ⁴² has a carboxy group as a substituent; and at least one of R ³⁹ to R ⁴² is an optionally substituted aromatic hydrocarbon group with 6 to 20 carbon atoms. and the methylene group contained in the aliphatic hydrocarbon group may be replaced with -O-. ]

The alkyl groups having 1 to 20 carbon atoms represented by R ³¹ to R ³⁸ may be linear, branched or cyclic. Specific examples of linear or branched alkyl groups include methyl group, ethyl group, propyl group, isobutyl group, butyl group, tert-butyl group, hexyl group, heptyl group, octyl group, nonyl group, A decyl group, a heptadecyl group, an undecyl group and the like can be mentioned. Cyclic alkyl groups include cyclopropyl, 1-methylcyclopropyl, cyclopentyl, cyclohexyl, 1,2-dimethylcyclohexyl, cyclooctyl, 2,4,6-trimethylcyclohexyl, and 4-cyclohexylcyclohexyl. and the like.
Examples of substituents of the alkyl groups having ¹ to 20 carbon atoms represented by R ³¹ to R ³⁸ include halogen atoms such as fluorine, chlorine, ^bromine and iodine atoms; ^hydroxy group; and R ^l are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; a methoxycarbonyl group and an ethoxycarbonyl group An alkoxycarbonyl group having 1 to 10 carbon atoms such as;

The alkoxy groups having 1 to 20 carbon atoms represented by R ³¹ to R ³⁸ include groups in which —O— is bonded to the bond of the above alkyl groups having 1 to 20 carbon atoms. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group , 2-ethylhexyloxy group and the like.
Substituents for the alkoxy groups having 1 to 20 carbon atoms represented by R ³¹ to R ³⁸ include ^halogen atoms such as fluorine, chlorine, ^bromine and iodine atoms; ^hydroxy groups; and R ⁿ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; a methoxycarbonyl group and an ethoxycarbonyl group An alkoxycarbonyl group having 1 to 10 carbon atoms such as;
The number of carbon atoms in the alkyl group and alkoxy group having 1 to 20 carbon atoms represented by R ³¹ to R ³⁸ is preferably 1 to 15, more preferably 1 to 10, still more preferably 1 to 5.

Among R ³¹ to R ³⁸ , R ³¹ to R ³⁴ are particularly preferably hydrogen atoms. R ³⁵ to R ³⁸ each independently represent a hydrogen atom, a hydroxy group, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted C 1 to 20 alkoxy groups are preferred, and hydrogen atoms or hydroxy groups are more preferred.

Two to four of R ³¹ to R ³⁸ (preferably R ³⁵ to R ³⁸ ) are preferably each independently a hydroxy group, and R ³¹ to R ³⁸ (preferably R ³⁵ to R ³⁸ ) It is more preferable that 2 to 3 of them are each independently hydroxy groups, and 2 of R ³¹ to R ³⁸ (preferably R ³⁵ to R ³⁸ ) are each independently hydroxy groups. is more preferred.

Examples of the hydrocarbon groups having 1 to 20 carbon atoms represented by R ³⁹ to R ⁴² include aliphatic hydrocarbon groups having 1 to 20 carbon atoms and aromatic hydrocarbon groups having 6 to 20 carbon atoms.

The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be either saturated or unsaturated, preferably saturated. The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear, branched or cyclic, preferably linear or branched.

Linear or branched aliphatic hydrocarbons having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, vinyl group, 1- straight chain aliphatic hydrocarbon groups such as propenyl group and 2-propenyl group (allyl group); branched chain aliphatic hydrocarbon groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; mentioned. The aliphatic hydrocarbon group preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 5 carbon atoms.
A cyclic aliphatic hydrocarbon group may be monocyclic or polycyclic. The cyclic aliphatic hydrocarbon group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like. The number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 3-8, more preferably 3-6.

A methylene group contained in the aliphatic hydrocarbon group having 1 to 20 carbon atoms may be replaced with -O-. Examples of the group in which the methylene group contained in the aliphatic hydrocarbon group is replaced with -O- include groups represented by the following formulae. In the following formula, * represents a bond.

Examples of aromatic hydrocarbon groups having 6 to 20 carbon atoms include phenyl group, xylyl group, trimethylphenyl group, dipropylphenyl group, di(2,2-dimethylpropyl)phenyl group, naphthyl group and the like. The aromatic hydrocarbon group preferably has 6 to 16 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 to 9 carbon atoms.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ³⁹ to R ⁴² may have a substituent, and the substituent may be a carboxy group; a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. alkoxy group having 1 to 10 carbon atoms such as methoxy group and ethoxy group; hydroxy group; sulfamoyl group; alkoxycarbonyl group having 1 to 10 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group;

At least one of R ³⁹ to R ⁴² is an aliphatic hydrocarbon group having 1 to 20 carbon atoms and having a carboxy group as a substituent. The aliphatic hydrocarbon group having 1 to 20 carbon atoms and having a carboxy group as a substituent preferably has 1 to 2 carboxy groups, more preferably 1 carboxy group. Moreover, the carboxy group is preferably bonded to at least the terminal of an aliphatic hydrocarbon group having 1 to 20 carbon atoms having a carboxy group as a substituent. Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms having a carboxy group as a substituent include groups represented by the following formulae. In the following formula, * represents a bond.

At least one of R ³⁹ to R ⁴² is an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. The optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms is preferably a phenyl group, a xylyl group, a trimethylphenyl group, a dipropylphenyl group, and di(2,2-dimethylpropyl). a phenyl group or; a phenyl group having two halogen atoms as substituents, such as a 2,4-difluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, and 2,4-diiodophenyl group; , and more preferably a 2,4-dimethylphenyl group, a 2,4,6-trimethylphenyl group or a 2,4-difluorophenyl group.

In compound (III), R ³⁹ and R ⁴² are each independently a C 1-20 aliphatic hydrocarbon group having a carboxy group as a substituent, and R ⁴⁰ and R ⁴¹ are each independently substituted It is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a group,
R ³⁹ and R ⁴² are each independently a C 1-10 aliphatic hydrocarbon group having a carboxy group as a substituent, and R ⁴⁰ and R ⁴¹ are each independently a substituent; more preferably an aromatic hydrocarbon group having 6 to 16 carbon atoms,
R ³⁹ and R ⁴² are each independently a C 1-8 aliphatic hydrocarbon group having a carboxy group as a substituent, and R ⁴⁰ and R ⁴¹ are each independently a substituent; more preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms,
R ³⁹ and R ⁴² are each independently a C 1-5 aliphatic hydrocarbon group having a carboxy group as a substituent, and R ⁴⁰ and R ⁴¹ are each independently a substituent; It is even more preferably an aromatic hydrocarbon group having 6 to 9 carbon atoms.
Compound (III) preferably has 2 to 4 hydroxy groups and 2 to 4 carboxy groups, more preferably 2 to 3 hydroxy groups and 2 to 3 carboxy groups, even more preferably 2 hydroxy groups. and two carboxy groups.

Examples of compound (III) include compounds represented by formulas (III-1) to (III-180) shown in Tables 13 to 15, and the like.
Compound (III) is
Preferred are compounds represented by formulas (III-1) to (III-90) and formulas (III-121) to (III-180),
More preferred are compounds represented by formulas (III-1) to (III-30) and formulas (III-121) to (III-150),
More preferably, compounds represented by formulas (III-1) to (III-3), formulas (III-19) to (III-21), and formulas (III-127) to (III-129) can be,
Compounds represented by formulas (III-1) to (III-3) are more preferred, and compounds represented by formula (III-3) are particularly preferred.

In Tables 13 to 15, ph1 to ph10 represent groups represented by the following formulas (* means a bond).

In Tables 13 to 15, ca1 to ca6 represent groups represented by the following formulas (* means a bond).

The compound represented by formula (III) can be synthesized, for example, by the method described in JP-A-2019-163233.

The squarylium dye preferably contains at least one selected from the group consisting of compound (I) and compound (III).

The content of compound (I) and compound (III) is preferably 0.1 to 150 parts by mass, more preferably 0.3 to 100 parts by mass, relative to 100 parts by mass of resin (B). It is preferably 0.5 to 50 parts by mass, and more preferably 0.5 to 50 parts by mass.

The content of compound (I) and compound (III) is preferably 20% by mass or more, more preferably 50% by mass or more, and 80% by mass or more in the total amount of the colorant (A). is more preferable, and 90% by mass or more is particularly preferable.

The content of the squarylium dye is 3 to 140 parts by mass, more preferably 5 to 130 parts by mass, still more preferably 10 to 120 parts by mass, relative to 100 parts by mass of the polymerization initiator (D). Within this range, a color filter with good contrast can be obtained.
When the squarylium dye is compound (I) (including compound (II)), the content of compound (I) is preferably 3 to 140 parts by mass with respect to 100 parts by mass of the polymerization initiator (D). More preferably 18 to 135 parts by mass, still more preferably 50 to 130 parts by mass, still more preferably 90 to 125 parts by mass. When the squarylium dye is compound (I), contrast tends to improve as the content of compound (I) relative to polymerization initiator (D) increases.
When the squarylium dye is compound (III), the content of compound (III) is preferably 3 to 140 parts by mass, more preferably 18 to 135 parts by mass, relative to 100 parts by mass of the polymerization initiator (D). , More preferably 50 to 130 parts by mass, and even more preferably 90 to 125 parts by mass. When the squarylium dye is compound (III), contrast tends to improve as the content of compound (III) relative to polymerization initiator (D) increases.

Colorant (A) may contain a colorant different from compound (I) and compound (III) in addition to compound (I) and compound (III). The coloring agent different from compound (I) and compound (III) may be either a dye (hereinafter sometimes referred to as dye (A1)) or a pigment (hereinafter sometimes referred to as pigment (A2)). . Colorants different from compound (I) and compound (III) may contain one or both of these dyes (A1) and pigments (A2).

Dye (A1) is not particularly limited as long as it does not include compound (I) and compound (III), and known dyes can be used, including solvent dyes, acid dyes, direct dyes, mordant dyes, and the like. Dyes include, for example, compounds classified as having hues other than pigments in the Color Index (published by The Society of Dyers and Colourists), and known dyes described in Staining Note (Shikisensha). be done. Further, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes (provided that compound (I) and excluding compound (III)), acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes. Among these, organic solvent-soluble dyes are preferred.

Specifically, C.I. I. Solvent Yellow 4 (hereinafter, the description of C.I. Solvent Yellow is omitted and only the number is described.), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99 , 117, 162, 163, 167, 189;
C. I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86;
C. I. solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;
C. I. solvent blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
C. I. C.I. I. solvent dyes;
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;
C. I. acid blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;
C. I. acid green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109 and the like. I. acid dyes;
C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;
C. I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like. I. direct dyes;
C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse Violet 26, 27;
C. I. C.I. I. disperse dyes;
C. I. Basic Red 1, 10;
C. I. basic blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89;
C. I. Basic Violet 2;
C. I. basic red 9;
C. I. Basic Green 1 and other C.I. I. basic dyes;
C. I. Reactive Yellow 2,76,116;
C. I. Reactive Orange 16;
C. I. C.I. I. reactive dyes;
C. I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern Tread 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38 , 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;
C. I. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Modant Violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28 , 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58;
C. I. Modant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83, 84;
C. I. C.I. I. modant dyes;
C. I. C.I. I. and vat dyes.
These dyes may be appropriately selected according to the spectral spectrum of the desired color filter.

The pigment (A2) is not particularly limited, and known pigments can be used. Examples thereof include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists).
Examples of pigments include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as Pigment Blue 15, 15:3, 15:4, 15:6, 60; C.I. I. Violet color pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as Pigment Green 7, 36, 58;
C. I. Brown pigments such as Pigment Brown 23, 25;
C. I. Black pigments such as Pigment Black 1 and 7 are included.

If necessary, the pigment is subjected to rosin treatment, surface treatment using a pigment derivative into which an acidic group or basic group is introduced, graft treatment to the pigment surface with a polymer compound, etc., atomization by a sulfuric acid atomization method, etc. Treatment, washing treatment with an organic solvent, water, or the like for removing impurities, removal treatment by an ion exchange method for ionic impurities, or the like may be performed.
The pigment preferably has a uniform particle size. A pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained by incorporating the pigment dispersant and performing the dispersion treatment.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more. As pigment dispersants, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA), Ajisper (Ajinomoto Fine Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie), and the like.
When a pigment dispersant is used, the amount used is preferably 1% by mass or more and 100% by mass or less, more preferably 5% by mass or more and 50% by mass or less, relative to the total amount of the pigment (A2). When the amount of the pigment dispersant used is within the above range, there is a tendency to obtain a uniformly dispersed pigment dispersion.

The content of the colorant (A) in the colored curable resin composition is preferably 0.1% by mass or more and 70% by mass or less, more preferably 0.5% by mass or more and 60% by mass, relative to the total amount of solids. % by mass or less, more preferably 1% by mass or more and 50% by mass or less.
In addition, the content of the squarylium dye in the colored curable resin composition is preferably 0.1% by mass or more and 40% by mass or less, more preferably 0.5% by mass or more and 30% by mass, relative to the total amount of solids. % or less, more preferably 1 mass % or more and 20 mass % or less.
When the content of the coloring agent (A) and the squarylium dye is within the above range, the color density of the color filter is sufficient, and the composition contains the resin (B) and the polymerizable compound (C). Since it can be contained in a necessary amount, a pattern with sufficient mechanical strength can be formed.

Here, the "total amount of solid content" in this specification refers to the amount obtained by subtracting the content of the solvent from the total amount of the colored curable resin composition. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography.

<Resin (B)>
The resin (B) is preferably an alkali-soluble resin and contains at least one monomer selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter, "monomer (a)" It is more preferable that the polymer has a structural unit derived from
The resin (B) is a structural unit derived from a monomer having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b)"), and A copolymer having other structural units is preferred.
Other structural units include a monomer copolymerizable with the monomer (a) (but different from the monomer (a) and the monomer (b). Hereinafter, "monomer (c) ”), structural units having an ethylenically unsaturated bond, and the like.

As used herein, "(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 monomer (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and o-, m-, p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;
methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1]hept-2-ene and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other bicyclounsaturated compounds containing a carboxy group;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- unsaturated dicarboxylic anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride;
Unsaturated mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate ;
unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid;

Among these, acrylic acid, methacrylic acid, o-, m-, p-vinylbenzoic acid, maleic anhydride, and the like are preferable in terms of copolymerization reactivity and solubility of the resulting resin in an aqueous alkaline solution.

The monomer (b) has a cyclic ether structure having 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring (oxolane ring)) and an ethylenically unsaturated bond. A polymerizable compound having
Monomer (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

As the monomer (b), for example, a monomer having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b1)"), an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b2)"), a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as "monomer (b3)" in some cases), etc.

As the monomer (b1), for example, a monomer having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (hereinafter, "monomer (b1-1)" (sometimes referred to as "monomer (b1-2)"), and a monomer having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized (hereinafter sometimes referred to as "monomer (b1-2)").

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

Examples of the monomer (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (eg, Celloxide (registered trademark) 2000; manufactured by Daicel Corporation), 3,4-epoxy Cyclohexylmethyl (meth)acrylate (e.g., Cychromer (registered trademark) A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cychromer (registered trademark) M100; Daicel Corporation) (manufactured), a compound represented by formula (BI), a compound represented by formula (BII), and the like.

[In formula (BI) and formula (BII), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group. may be substituted with
X ^a and X ^b each independently represent a single bond, *-R ^c -, *-R ^c -O-, *-R ^c -S- or *-R ^c -NH-.
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* represents a bond with O. ]

Examples of alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.

Alkyl groups in which a hydrogen atom is substituted with hydroxy include, for example, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1 -hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.

R ^a and R ^b preferably include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.

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, A hexane-1,6-diyl group and the like can be mentioned.

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 and *--CH ₂ CH ₂ --O-- (* represents a bond with O).

Examples of the compound represented by formula (BI) include compounds represented by any one of formulas (BI-1) to (BI-15). Among them, formula (BI-1), formula (BI-3), formula (BI-5), formula (BI-7), formula (BI-9) and formula (BI-11) to formula (BI-15) Compounds represented by Formula (BI-1), Formula (BI-7), Formula (BI-9) and Formula (BI-15) are more preferable.

Examples of the compound represented by formula (BII) include compounds represented by any one of formulas (BII-1) to (BII-15), and among them, preferably formula (BII-1), formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9) and compounds represented by formulas (BII-11) to (BII-15), and more Preferred are compounds represented by formula (BII-1), formula (BII-7), formula (BII-9) and formula (BII-15).

The compound represented by Formula (BI) and the compound represented by Formula (BII) may be used alone, or two or more of them may be used in combination. The compound represented by formula (BI) and the compound represented by formula (BII) may be used in combination. When the compound represented by the formula (BI) and the compound represented by the formula (BII) are used in combination, the content ratio [compound represented by the formula (BI): compound represented by the formula (BII)] is On a molar basis, the ratio is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, still more preferably 20:80 to 80:20.

As the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferred.
Examples of the monomer (b2) include 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, 3-methyl-3-(meth)acryloyl oxyethyloxetane, 3-ethyl-3-(meth)acryloyloxyethyloxetane and the like.

As the monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable.
Examples of the monomer (b3) include tetrahydrofurfuryl acrylate (eg, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As the monomer (b), the monomer (b1) is preferable in that the heat resistance, chemical resistance, etc. of the obtained color filter can be further improved. Furthermore, the monomer (b1-2) is more preferable in terms of excellent storage stability of the coloring composition.

Examples of the monomer (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2. 1.0 ^2,6 ]decane-8-yl (meth)acrylate (in the technical field, it is commonly referred to as “dicyclopentanyl (meth)acrylate”. Also, “tricyclodecyl (meth)acrylate ”), tricyclo[5.2.1.0 ^2,6 ]decan-9-yl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth ) acrylate (commonly referred to as “dicyclopentenyl (meth)acrylate” in the technical field), tricyclo[5.2.1.0 ^2,6 ]decen-9-yl (meth)acrylate, di Cyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate and benzyl (meth)acrylate (meth)acrylic acid esters such as acrylates;
Hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;
Halogen atom-containing (meth)acrylic acid esters such as 2,2,3,3,4,4,5,5-octafluoropentyl (meth)acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;
bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5- Hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2′-hydroxyethyl)bicyclo[2.2.1] Hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2 .1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2′-hydroxyethyl)bicyclo[2.2. 1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy -5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2 .2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene and 5,6-bis(cyclohexyl oxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 - dicarbonylimide derivatives such as maleimidopropionate and N-(9-acridinyl)maleimide;
vinyl group-containing aromatic compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, 9-vinylcarbazole and p-methoxystyrene; vinyl group-containing nitriles such as (meth)acrylonitrile; Halogenated hydrocarbons such as vinyl and vinylidene chloride; vinyl group-containing amides such as (meth)acrylamide; esters such as vinyl acetate; dienes such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene ; and the like.
Among these, styrene, vinyl toluene, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate, tricyclo[5.2.1 .0 ^2,6 ]decane-9-yl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate, tricyclo[5.2.1.0 ^{2, 6} ] Decen-9-yl (meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, phenyl (meth)acrylate, 2,2 , 3,3,4,4,5,5-octafluoropentyl (meth)acrylate, 9-vinylcarbazole, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate and 2-ethylhexyl (meth)acrylate, etc. preferable.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ] Decyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/benzyl (meth)acrylate/(meth) Acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl(meth)acrylate/9-vinylcarbazole/(meth)acrylic acid copolymer, 3,4-epoxy Tricyclo[5.2.1.0 ^2,6 ]decyl(meth)acrylate/phenyl(meth)acrylate/o-vinylbenzoic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/phenyl (meth)acrylate/m-vinylbenzoic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/ Phenyl (meth)acrylate/p-vinylbenzoic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/phenyl (meth)acrylate/(meth)acrylic Acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/2,2,3,3,4,4,5,5-octafluoropentyl ( meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate/styrene/(meth)acrylic acid copolymer , 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl(meth)acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5. 2.1.0 ^2,6 ]decyl (meth)acrylate/(meth)acrylic acid/N-cyclohexylmaleimide/2-hydroxyethyl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2. 1.0 ^2,6 ]decyl (meth)acrylate/(meth)acrylic acid/vinyl toluene copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/ (Meth)acrylic acid/2-ethylhexyl (meth)acrylate copolymer 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/tricyclo[5.2.1.0 ^2,6 ]decenyl (meth)acrylate/(meth)acrylic Acid/N-cyclohexylmaleimide copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer, benzyl(meth)acrylate/(meth)acrylic acid copolymer , styrene/(meth)acrylic acid copolymers, and resins described in JP-A-9-106071, JP-A-2004-29518 and JP-A-2004-361455.
Among them, as the resin (B), a copolymer containing a structural unit derived from the monomer (a) and a structural unit derived from the monomer (b) is preferable.

The resin (B) may be a combination of two or more. In this case, the resin (B) contains at least
It preferably contains at least one copolymer containing a structural unit derived from the monomer (a) and a structural unit derived from the monomer (b),
More preferably, at least one copolymer containing a structural unit derived from the monomer (a) and a structural unit derived from the monomer (b1) is included,
More preferably, at least one copolymer containing a structural unit derived from the monomer (a) and a structural unit derived from the monomer (b1-2) is included,
3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^{2 ,6} ] Decyl (meth)acrylate/(meth)acrylic acid/N-cyclohexylmaleimide/2-hydroxyethyl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ] Decyl (meth)acrylate/(meth)acrylic acid/vinyl toluene copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/(meth)acrylic acid/ More preferably, it contains one or more selected from 2-ethylhexyl (meth)acrylate copolymers.

The polystyrene equivalent weight average molecular weight (Mw) of the resin (B) is preferably 1,000 or more and 100,000 or less, more preferably 2,000 or more and 50,000 or less, and still more preferably 3,000 or more. It is 30,000 or less, and more preferably 5,000 or more and 30,000 or less. When the weight-average molecular weight is within the above range, the unexposed area tends to have high solubility in a developer, and the resulting pattern tends to have a high residual film rate and hardness.

The dispersion degree [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, and still more preferably 1 or more and 4 or less. is.

The acid value (solid content conversion value) of the resin (B) is preferably 10 mg-KOH/g or more and 300 mg-KOH/g or less, more preferably 20 mg-KOH/g or more and 250 mg-KOH/g or less, More preferably 25 mg-KOH/g or more and 200 mg-KOH/g or less, still more preferably 30 mg-KOH/g or more and 180 mg-KOH/g or less, particularly preferably 40 mg-KOH/g or more and 150 mg-KOH/g g or less. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined by titration with an aqueous potassium hydroxide solution, for example.

The content of the resin (B) is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 13% by mass with respect to 100% by mass of the solid content of the colored curable resin composition. 70% by mass, more preferably 15 to 60% by mass. When the content of the resin (B) is within the above range, the solubility of the unexposed area in the developing solution tends to be high.

<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). Examples thereof include compounds having a polymerizable ethylenically unsaturated bond, preferably It is a (meth)acrylic acid ester compound.

The average number of ethylenically unsaturated group equivalents of the polymerizable compound (C) is less than 96.0. As a result of investigation by the present inventors, it has been found that if the average number of ethylenically unsaturated group equivalents exceeds the above range, the contrast of the color filter deteriorates.
The average ethylenically unsaturated group equivalent number of the polymerizable compound (C) is preferably 95.5 or less, more preferably 95.0 or less, even more preferably 94.5 or less, and even more preferably 94.0 or less. Although the lower limit is not particularly limited, the average ethylenically unsaturated group equivalent number of the polymerizable compound (C) is preferably 83.0 or more, more preferably 83.5 or more, further preferably 84.0 or more, and 84.5. The above is more preferable, and 85.0 or more is particularly preferable.
In addition, the average ethylenically unsaturated group equivalent number of the polymerizable compound (C) is calculated from the formula (1).

<Average ethylenically unsaturated group equivalent number>
The average ethylenically unsaturated group equivalent number of the polymerizable compound (C) is represented by the formula (1).
Average number of ethylenically unsaturated group equivalents of the polymerizable compound (C) = _{ΣK i} mi (1)
[In formula (1),
K _i : A value represented by (molecular weight/number of ethylenically unsaturated bonds) of component i among all polymerizable compounds (C) contained in the colored curable resin composition.
m _i : represents the mole fraction of the i component. ]

The polymerizable compound (C) preferably contains a polymerizable compound having 3 or more (preferably 5 or less, more preferably 4 or less) ethylenically unsaturated bonds.
As the polymerizable compound, any polymerizable compound can be used as long as the average number of ethylenically unsaturated group equivalents of the polymerizable compound (C) satisfies less than 96.0. Examples of the polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerin tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, di Pentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate ) 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, and caprolactone-modified dipentaerythritol hexa(meth)acrylate.
Among them, the polymerizable compound (C) preferably contains at least one selected from pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate and glycerin tri(meth)acrylate, pentaerythritol triacrylate, More preferably, it contains at least one selected from pentaerythritol tetraacrylate and glycerin triacrylate.

The polymerizable compound (C) may be a combination of two or more of the above examples, or may be a combination of pentaerythritol tri(meth)acrylate and pentaerythritol tetra(meth)acrylate.

When pentaerythritol tri(meth)acrylate and pentaerythritol tetra(meth)acrylate are combined, the ratio (x:y) of pentaerythritol tri(meth)acrylate (x) and pentaerythritol tetra(meth)acrylate (y) is preferably is 1 to 99 mol%: 99 to 1 mol%, more preferably 10 to 90 mol%: 90 to 10 mol%, more preferably 20 to 80 mol%: 80 to 20 mol%, still more preferably 30 to 70 Mole %: 70 to 30 mol %.

The content of the polymerizable compound (C) is preferably 1 to 65% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 55% by mass, based on the total solid content. Yes, more preferably 15% by mass or more, 20% by mass or more, or 25% by mass or more. When the content of the polymerizable compound (C) is within the above range, there is a tendency that the residual film ratio at the time of forming the colored pattern and the chemical resistance of the color filter are improved. Further, when the content is increased within the above range, the contrast tends to be further improved.

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

Examples of the 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-acetyloxy-1-(4-phenylsulfanylphenyl )-O-acyloxime compounds having a diphenylsulfide skeleton such as 3-cyclohexylpropan-1-one-2-imine; N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) Benzoyl}-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane -1-imine, carbazole such as N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine O-acyloxime compounds having a skeleton; O-acyloximes having a fluorene skeleton such as 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]ethanone O-acetyloxime compounds; and the like. Irgacure (registered trademark) OXE01, OXE02 (manufactured by BASF), PBG-327 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), N-1919 (manufactured by ADEKA), DFI-091 (manufactured by Daito Chemix Co., Ltd.) You may use commercial items, such as. Among them, O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfanylphenyl)-3- Cyclohexylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl}-9H-carbazol-3-yl]ethan-1-imine and 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]ethanone O-acetyloxime At least one selected from the group is preferred. These O-acyl oxime compounds tend to give high-brightness color filters.

Examples of the alkylphenone compounds include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane, -1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one, 2-hydroxy-2-methyl- 1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl -1-(4-isopropenylphenyl)propan-1-one oligomer, α,α-diethoxyacetophenone, benzyl dimethyl ketal and the like. Commercially available products such as Irgacure (registered trademark) 369, 907, 379 (manufactured by BASF) may also be used.

Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4- methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxy styryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4 -bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino- 2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc. are mentioned.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may also be used.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)- 4,4',5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis(2-chlorophenyl)-4 ,4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetra(alkoxyphenyl)biimidazole, 2,2′-bis (2-chlorophenyl)-4,4′,5,5′-tetra(dialkoxyphenyl)biimidazole, 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetra(tri alkoxyphenyl)biimidazole (see, for example, JP-B-48-38403, JP-A-62-174204, etc.), the phenyl groups at the 4,4′,5,5′-positions are substituted with carboalkoxy groups; and biimidazole compounds (see, for example, JP-A-7-10913).

Polymerization initiators that generate acids include, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxy Onium salts such as phenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylates, benzoin tosylates and the like.

Furthermore, the polymerization initiator (D) includes benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3′,4,4′-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like.

As the polymerization initiator (D), a polymerization initiator containing at least one selected from the group consisting of O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds and biimidazole compounds is preferred, and O-acyloxy More preferred is a polymerization initiator containing a chromium compound.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 205 parts by mass, with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). part by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, thereby improving the productivity of the color filter.

The content of the polymerization initiator (D) is preferably 1 to 70 parts by mass, more preferably 2 to 65 parts by mass, still more preferably 3 to 60 parts by mass, relative to 100 parts by mass of the polymerizable compound (C). More preferably, it is 55 parts by mass or less, 50 parts by mass or less, 45 parts by mass or less, 40 parts by mass or less, 35 parts by mass or less, 30 parts by mass or less, or 25 parts by mass or less. When the content of the polymerization initiator (D) is within the above range, the contrast tends to be improved, and when it is reduced within the above range, the contrast tends to be further improved.

The content of the polymerization initiator (D) is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% by mass, still more preferably 1 to 20% by mass, more preferably 1 to 20% by mass, based on the total solid content. It is preferably 15% by mass or less, or 10% by mass or less. When the content of the polymerization initiator (D) is within the above range, the contrast tends to be improved, and when it is decreased within the above range, the contrast tends to be further improved.

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

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 -2-ethylhexyl dimethylaminobenzoate, N,N-dimethyl p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis (Ethylmethylamino)benzophenone and the like can be mentioned, and 4,4′-bis(diethylamino)benzophenone is preferred among them. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may also be used.

Examples of the alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-di butoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene and the like.

The thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

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

When using these polymerization initiation aids (D1), the content is preferably 0.1 to 30 parts by mass, with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is preferably 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of color filters tends to improve.

<Solvent (E)>
The solvent (E) is not particularly limited, and solvents commonly used in the field can be used. For example, ester solvent (solvent containing -COO- in the molecule but not containing -O-), ether solvent (solvent containing -O- in the molecule but not containing -COO-), ether ester solvent (solvent containing -COO- in the molecule solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule but not containing -COO-), alcohol solvent (containing OH in the molecule, -O-, - solvents that do not contain CO— and —COO—), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide.

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

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

Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl Ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like.

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.

Alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.

Aromatic hydrocarbon solvents include benzene, toluene, xylene and mesitylene.

Amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

Among the above solvents, organic solvents having a boiling point of 120° C. or higher and 180° C. or lower at 1 atm are preferable from the viewpoint of coating properties and drying properties. Solvents include propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone. and N,N-dimethylformamide are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethyl lactate and ethyl 3-ethoxypropionate are more preferred.

The content of the solvent (E) is preferably 70-95% by mass, more preferably 75-92% by mass, relative to the total amount of the colored curable resin composition of the present invention. In other words, the total 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 within the above range, the flatness at the time of coating is improved, and when a color filter is formed, the color density is not insufficient, so the display characteristics tend to be improved. .

<Leveling agent (F)>
Examples of the leveling agent (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymerizable group in the side chain.
Examples of silicone-based surfactants include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray SH7PA, Toray DC11PA, Toray SH21PA, Toray SH28PA, Toray SH29PA, Toray SH30PA, Toray SH8400 (manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan LLC) and the like.

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

Examples of the fluorine atom-containing silicone-based surfactants include surfactants having siloxane bonds and fluorocarbon chains in the molecule. Specifically, Megafac (registered trademark) R08, Megafac BL20, Megafac F475, F477 and F443 (manufactured by DIC Corporation) and the like can be mentioned.

The content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.2% by mass or less, relative to the total amount of the colored curable resin composition. It is 2 mass % or less, more preferably 0.005 mass % or more and 0.2 mass % or less. This content does not include the content of the dispersant. 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 may optionally contain additives known in the art such as polymerization initiation aids, fillers, other polymer compounds, adhesion promoters, light stabilizers, chain transfer agents, and the like. agent.
Adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane. Ethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane , 3-isocyanatopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-( aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltriethoxysilane Silane etc. are mentioned.

<Method for producing colored curable resin composition>
The colored curable resin composition includes, for example, a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and optionally used a solvent (E), a leveling agent ( It can be prepared by mixing F), the polymerization initiation aid (D1) and other components.
The colorant (A) may be included in the pigment dispersion in advance. The desired colored curable resin composition can be prepared by mixing the pigment dispersion with the remaining components so as to have a predetermined concentration.
When a dye is contained, the dye may be dissolved in part or all of the solvent (E) in advance to prepare a solution. It is preferable to filter the solution through a filter having a pore size of about 0.01 to 1 μm.
It is preferable to filter the colored curable resin composition after mixing through a filter having a pore size of about 0.01 to 10 μm.

<Color filter>
Examples of the method for producing a colored pattern of a color filter from the colored curable resin composition of the present invention include a photolithography method, an inkjet method, a printing method and the like. Among them, the photolithographic method is preferred. Photolithography is a method in which the colored curable resin composition is applied to a substrate, dried to form a composition layer, exposed through a photomask, and developed. In the photolithographic method, a colored coating film, which is a cured product of the composition layer, can be formed by not using a photomask during exposure and/or not developing.

The film thickness of the color filter (cured film) is, for example, 30 µm or less, preferably 20 µm or less, more preferably 6 µm or less, even more preferably 3 µm or less, still more preferably 1.5 µm or less, and particularly preferably 0.5 µm or less. It is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more.

Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass whose surface is coated with silica; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; A thin film of aluminum, silver, silver/copper/palladium alloy, etc. is formed on the substrate. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates. Alternatively, a substrate obtained by subjecting a silicon substrate to HMDS processing may be used.

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

The composition layer is then exposed through a photomask to form the desired colored pattern. The pattern on the photomask is not particularly limited, and a pattern suitable for the intended use is used. The light source used for exposure is preferably a light source that emits light with a wavelength of 250 to 450 nm. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. You can Specifically, mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, and the like can be used. Since it is possible to uniformly irradiate the entire exposure surface with parallel light rays and to perform accurate alignment between the photomask and the substrate, it is possible to use a reduction projection exposure apparatus such as a mask aligner and a stepper, or a proximity exposure apparatus. preferable.

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

Furthermore, it is preferable to post-bake the obtained colored pattern. The post-baking temperature is preferably 80 to 250°C, more preferably 100 to 245°C. Post-baking time is preferably 1 to 120 minutes, more preferably 2 to 30 minutes.

The colored pattern and colored coating film thus obtained are useful as a color filter, and the color filter is used in display devices (e.g., liquid crystal display devices, organic EL devices, etc.), electronic paper, solid-state imaging devices, and the like. It is useful as a color filter used.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples. In the examples, percentages and parts representing contents or usage amounts are based on mass unless otherwise specified.

[Synthesis Example 1]
A compound represented by formula (II-135) was obtained according to Example 8 described in JP-A-2020-055956.

[Synthesis Example 2]
A compound represented by formula (III-3) was obtained according to Example 2 described in JP-A-2019-163233.

[Resin Synthesis Example 1]
A suitable amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to create a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and the flask was heated to 80°C while stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^{2, 6} ] A mixed solution of 289 parts of a mixture of decane-9-yl acrylate (mixing ratio is 1:1) and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a mixed solution of 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the completion of dropping, the contents of the flask were held at 80° C. for 4 hours and then cooled at room temperature to form a copolymer having a B-type viscosity (23° C.) of 125 mPa s and a solid content of 35.1% (resin (B-1) ) to give a solution. The resulting copolymer had a weight average molecular weight Mw of 9200, a dispersity of 2.08 and a solid content acid value of 77 mg-KOH/g. Resin (B-1) has the following structural units.

The polystyrene equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.
Apparatus; HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature; 40°C
Solvent; THF
Flow rate; 1.0 mL/min
Test liquid solid content concentration; 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Standard material for calibration; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(manufactured by Tosoh Corporation)
The ratio (Mw/Mn) of the polystyrene-equivalent weight-average molecular weight and the number-average molecular weight obtained above was defined as the degree of dispersion.

[Examples 1 to 24, Comparative Example 1]
[Preparation of colored curable resin composition]
Each component was mixed so as to have the composition shown in Tables 16 and 17 to obtain a colored curable resin composition.
In Tables 16 and 17, each component represents the following compounds.
Coloring agent (A-1): compound represented by formula (II-135) Coloring agent (A-2): compound represented by formula (III-3) Resin (B-1): resin (B-1 ) (solid content conversion)
Polymerizable compound (C-1): pentaerythritol tetraacrylate (average ethylenically unsaturated group equivalent number 88.1; A-TMMT; manufactured by Shin-Nakamura Chemical Co., Ltd.)
Polymerizable compound (C-2): pentaerythritol tri and pentaerythritol tetraacrylate (average ethylenically unsaturated group equivalent number 94.6; A-TMM-3LM-N; trifunctional about 57 mol%, tetrafunctional about mol 43 %; manufactured by Shin-Nakamura Chemical Co., Ltd.)
Polymerizable compound (C-3): glycerin triacrylate (average ethylenically unsaturated group equivalent 84.7; Aronix (registered trademark) M-930; manufactured by Toagosei Co., Ltd.)
Polymerizable compound (C-4): dipentaerythritol hexaacrylate (average ethylenically unsaturated group equivalent number 96.4; KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D-1): N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine (PBG-327; oxime compound; Changzhou Strong Electronic New Materials ( Co., Ltd.)
Polymerization initiator (D-2): 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]ethanone O-acetyloxime (DFI-091; oxime compound; Daito Chemix company)
Polymerization initiator (D-3): N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl} -9H-carbazol-3-yl]ethan-1-imine (N-1919; oxime compound; manufactured by ADEKA)
Solvent (E-1): 4-hydroxy-4-methyl-2-pentanone Solvent (E-2): Propylene glycol monomethyl ether acetate Leveling agent (F-1): Polyether-modified silicone oil (Toray Silicone SH8400; Toray manufactured by Dow Corning Co., Ltd.)

[Preparation of colored coating film]
On a 5 cm square glass substrate (Eagle 2000; manufactured by Corning), the colored curable resin composition was applied by spin coating so that the film thickness after post-baking was 2.0 μm, and then coated at 100° C. for 3 hours. A coloring composition layer was formed by pre-baking for 1 minute. After cooling, the colored composition layer was irradiated with light at an exposure dose of 100 mJ/cm ² (365 nm standard) in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). After that, post-baking was performed in an oven at 230° C. for 30 minutes to obtain a colored coating film.

[Contrast evaluation]
For the resulting colored coating film, a contrast meter (CT-1; Tsubosaka Electric Co., Ltd., color difference meter BM-5A; Topcon Co., Ltd., light source; F-10, polarizing film; Tsubosaka Electric Co., Ltd.) was used. , the contrast was measured with a blank value of 30,000. The results are shown in Tables 16-17.

According to the above, contrast is improved by using a predetermined amount of squarylium dye and a predetermined polymerizable compound as colorants. In addition, when the amount of the polymerizable compound is increased, and when the amount of the polymerization initiator is decreased, the contrast is further improved.

Claims (9)

Colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D),
The coloring agent (A) contains a squarylium dye,
The average ethylenically unsaturated group equivalent number represented by the formula (1) of the polymerizable compound (C) is less than 96.0,
The content of the squarylium dye in the colored curable resin composition is 3 to 140 parts by mass with respect to 100 parts by mass of the polymerization initiator (D).
<Average ethylenically unsaturated group equivalent number>
Average number of ethylenically unsaturated group equivalents of the polymerizable compound (C) = _{ΣK i} mi (1)
[In formula (1),
K _i : A value represented by (molecular weight/number of ethylenically unsaturated bonds) of component i among all polymerizable compounds (C) contained in the colored curable resin composition.
m _i : represents the mole fraction of the i component. ] 2. The colored curable resin composition according to claim 1, wherein said squarylium dye contains at least one selected from the group consisting of compounds represented by formula (I) and compounds represented by formula (III).

[in the formula (I),
R ¹ to R ⁸ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, or optionally having a substituent It represents an alkoxy group having 1 to 20 carbon atoms.
R ⁹ and R ¹⁰ each independently represent a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and the methylene group contained in the aliphatic hydrocarbon group is - O- may be substituted.
R ¹¹ and R ¹² each independently represent a hydrocarbon group having 6 to 20 carbon atoms and having an aromatic hydrocarbon ring, and the hydrocarbon group may have a substituent. The methylene group contained may be replaced with -O-.
R ¹³ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms. ]

[in the formula (III),
R ³¹ to R ³⁸ each independently represent a hydrogen atom, a hydroxy group, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted C 1 to 20 represents an alkoxy group.
R ³⁹ to R ⁴² each independently represent an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ³⁹ to R ⁴² has a carboxy group as a substituent; and at least one of R ³⁹ to R ⁴² is an optionally substituted aromatic hydrocarbon group with 6 to 20 carbon atoms. and the methylene group contained in the aliphatic hydrocarbon group may be replaced with -O-. ] 3. The colored curable resin composition according to claim 1, wherein the average ethylenically unsaturated group equivalent number is 83.0 or more. The colored curable resin composition according to any one of claims 1 to 3, wherein the polymerizable compound (C) comprises a polymerizable compound having 3 or more and 5 or less ethylenically unsaturated bonds. Any one of claims 1 to 4, wherein the polymerizable compound (C) comprises at least one selected from pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate and glycerin tri(meth)acrylate. Colored curable resin composition according to. The colored curable resin composition according to any one of claims 1 to 5, wherein the polymerization initiator (D) contains an O-acyloxime compound. A color filter formed from the colored curable resin composition according to any one of claims 1 to 6. A display device comprising the color filter according to claim 7 . A solid-state imaging device comprising the color filter according to claim 7 .