CN114815504A

CN114815504A - Colored curable resin composition

Info

Publication number: CN114815504A
Application number: CN202210085296.6A
Authority: CN
Inventors: 土谷崇夫
Original assignee: Sumitomo Chemical Co Ltd; Dongwoo Fine Chem Co Ltd; Sumika Technology Co Ltd
Current assignee: Sumitomo Chemical Co Ltd; Dongwoo Fine Chem Co Ltd; Sumika Technology Co Ltd
Priority date: 2021-01-28
Filing date: 2022-01-25
Publication date: 2022-07-29
Also published as: JP2022115798A; KR20220109332A; TW202233716A

Abstract

The purpose of the present invention is to provide a colored curable resin composition which is useful for producing a color filter having a good contrast. The colored curable resin composition of the present invention has the following characteristics: the colorant (A) contains a squarylium dye, the average number of equivalents of ethylenically unsaturated groups represented by formula (1) in the polymerizable compound (C) is less than 96.0, and the amount of the squarylium dye is 3 to 140 parts by mass per 100 parts by mass of the polymerization initiator (D).

Description

Colored curable resin composition

Technical Field

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

Background

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 CCDs 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 to 2.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2020 and 055956

Patent document 2: japanese patent laid-open publication No. 2019-163233

Disclosure of Invention

However, a color filter formed from a colored curable resin composition containing dipentaerythritol hexaacrylate may have an insufficient contrast.

The purpose of the present invention is to provide a colored curable resin composition which is useful for producing a color filter having a good contrast.

That is, the gist of the present invention is as follows.

[1] A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D),

the colorant (A) contains a squarylium dye,

the average number of equivalents of ethylenically unsaturated groups represented by formula (1) of the polymerizable compound (C) is less than 96.0,

the amount of the squarylium dye is 3 to 140 parts by mass per 100 parts by mass of the polymerization initiator (D).

< average number of equivalents of ethylenically unsaturated group >

The average number of equivalents of ethylenically unsaturated groups of the polymerizable compound (C) (. sigma.K) _i m _i …(1)

[ in the formula (1),

K _i the value represented by (molecular weight/number of ethylenically unsaturated bonds) of the i component in all the polymerizable compounds (C) contained in the colored curable resin composition is shown.

m _i Represents the mole fraction of the component i.]

[2] The colored curable resin composition according to [1], wherein the squarylium dye contains at least 1 selected from the group consisting of a compound represented by the formula (I) and a compound represented by the formula (III).

[ in the formula (I),

R ¹ ～R ⁸ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms which may have a substituent.

R ⁹ And R ¹⁰ Each independently represents a 2-valent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a methylene group contained in the aliphatic hydrocarbon group may be substituted by-O-.

R ¹¹ And R ¹² Each independently represents a hydrocarbon group having 6 to 20 carbon atoms and an aromatic hydrocarbon ring, the hydrocarbon group may have a substituent, and a methylene group contained in the hydrocarbon group may be substituted by-O-.

R ¹³ Represents a hydrogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms.]

[ in the formula (III),

R ³¹ ～R ³⁸ each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms which may have a substituent.

R ³⁹ ～R ⁴² Each independently represents a C1-20 hydrocarbon group which may have a substituent, R ³⁹ ～R ⁴² At least one of the above groups is an aliphatic hydrocarbon group having 1 to 20 carbon atoms and having a carboxyl group as a substituent, and R ³⁹ ～R ⁴² At least one of the aliphatic hydrocarbon groups is an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, and the methylene group contained in the aliphatic hydrocarbon group may be substituted by-O-.]

[3] The colored curable resin composition according to [1] or [2], wherein the average number of equivalents of the ethylenically unsaturated group 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 to 5 ethylenically unsaturated bonds.

[5] The colored curable resin composition according to any one of [1] to [4], wherein the polymerizable compound (C) contains at least 1 selected from pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and glycerol tri (meth) acrylate.

[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 comprising the colored curable resin composition according to any one of [1] to [6 ].

[8] A display device comprising the color filter of [7 ].

[9] A solid-state imaging element comprising the color filter according to [7 ].

According to the present invention, a colored curable resin composition useful for producing a color filter having a good contrast can be provided.

Detailed Description

The colored curable resin composition of the present invention contains a colorant (hereinafter, sometimes referred to as a colorant (a)), a resin (hereinafter, sometimes referred to as a resin (B)), a polymerizable compound (hereinafter, sometimes referred to as a polymerizable compound (C)), and a polymerization initiator (hereinafter, sometimes referred to as a polymerization initiator (D)).

The colorant (a) comprises a squarylium dye.

The colored curable resin composition of the present invention may contain a solvent (hereinafter, may be referred to as solvent (E)).

The colored curable resin composition of the present invention may contain a leveling agent (hereinafter, sometimes referred to as a leveling agent (F)).

In the present specification, the compounds exemplified as the respective components may be used alone or in combination of two or more unless otherwise specified.

< colorant (A) >

The colorant (a) comprises a squarylium dye. The squarylium dye can be any known dye without any particular limitation.

The squarylium dye preferably contains a compound represented by the formula (I) (hereinafter, may be referred to as compound (I)). The compound (I) includes the resonance structure of the formula (I), and also includes a compound obtained by further rotating each group in the formula (I) or the resonance structural formula thereof around the bond axis of a carbon-carbon single bond or a carbon-nitrogen single bond.

[ in the formula (I),

As R ¹ ～R ⁸ Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

R ¹ ～R ⁸ The saturated hydrocarbon group having 1 to 20 carbon atoms may be any of straight-chain, branched and cyclic. Specific examples of the linear or branched saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, and an isopropyl groupButyl, t-butyl, hexyl, heptyl, octyl, nonyl, decyl, heptadecyl, undecyl, and the like. Examples of the cyclic saturated hydrocarbon group include cyclopropyl, 1-methylcyclopropyl, cyclopentyl, cyclohexyl, 1, 2-dimethylcyclohexyl, cyclooctyl, 2,4, 6-trimethylcyclohexyl, and 4-cyclohexylcyclohexyl.

As R ¹ ～R ⁸ Examples of the substituent of the saturated hydrocarbon group having 1 to 20 carbon atoms include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group; -NR ^a R ^b (R ^a And R ^b Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; alkoxy groups having 1 to 10 carbon atoms such as methoxy and ethoxy; alkoxycarbonyl groups having 1 to 10 carbon atoms such as methoxycarbonyl and ethoxycarbonyl.

As R ¹ ～R ⁸ The alkoxy group having 1 to 20 carbon atoms includes a group in which-O-is bonded to the bonding site of the saturated hydrocarbon group having 1 to 20 carbon atoms. Specific examples thereof include 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, and 2-ethylhexyloxy group.

As R ¹ ～R ⁸ The substituent of the alkoxy group having 1 to 20 carbon atoms includes a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.; a hydroxyl group; -NR ^c R ^d (R ^c And R ^d Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; alkoxy groups having 1 to 10 carbon atoms such as methoxy and ethoxy; an alkoxycarbonyl group having 1 to 10 carbon atoms in an alkoxy moiety such as a methoxycarbonyl group or an ethoxycarbonyl group.

R ¹ ～R ⁸ The number of carbon atoms of the saturated hydrocarbon group is preferably 1 to 15, more preferably 1 to 10, still more preferably 1 to 7, and still more preferably 1 to 4.

R ¹ ～R ⁸ The saturated hydrocarbon group represented by (a) is preferably a linear or branched saturated hydrocarbon group, and more preferably a linear saturated hydrocarbon group.

R ¹ ～R ⁸ In, R ¹ ～R ⁴ Preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. In addition, R ¹ ～R ⁴ When it is a hydrogen atom or a methyl group, R is more preferable ¹ ～R ⁴ When it is a hydrogen atom, R ⁵ ～R ⁸ Each independently of the other, is preferably a hydrogen atom, a hydroxyl group, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms which may have a substituent, and more preferably a hydrogen atom or a hydroxyl group.

Preferably R ¹ ～R ⁸ (preferably R) ⁵ ～R ⁸ )2 to 4 of (a) are each independently a hydroxyl group, more preferably R ¹ ～R ⁸ (preferably R) ⁵ ～R ⁸ )2 to 3 of (a) are each independently a hydroxyl group, more preferably R ¹ ～R ⁸ (preferably R) ⁵ ～R ⁸ ) Each 2 of which is independently a hydroxyl group.

R ⁹ And R ¹⁰ The 2-valent aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by (a) may be either saturated or unsaturated, and is preferably saturated. The 2-valent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear, branched or cyclic, and is preferably linear or branched.

Examples of the aliphatic hydrocarbon group having a valence of 2 and having 1 to 20 carbon atoms include 2-valent straight-chain aliphatic hydrocarbon groups such as 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-1, 17-diyl group, and propenylene group; and 2-valent branched aliphatic hydrocarbon groups such as ethane-1, 1-diyl, propane-1, 2-diyl, propane-2, 2-diyl, pentane-2, 4-diyl, 2-methylpropane-1, 3-diyl, 2-methylpropane-1, 2-diyl, 2-dimethylpropane-1, 3-diyl, pentane-1, 4-diyl and 2-methylbutane-1, 4-diyl.

The cyclic 2-valent aliphatic hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic 2-valent aliphatic hydrocarbon group include monocyclic 2-valent aliphatic hydrocarbon groups such as cyclobutane-1, 3-diyl, cyclopentane-1, 3-diyl, cyclohexane-1, 4-diyl and cyclooctane-1, 5-diyl; and polycyclic aliphatic hydrocarbon groups having a valence of 2 such as norbornane-1, 4-diyl group, norbornane-2, 5-diyl group, adamantane-1, 5-diyl group, and adamantane-2, 6-diyl group.

R ⁹ And R ¹⁰ The number of carbon atoms of the 2-valent aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 7, and still more preferably 1 to 4.

R ⁹ And R ¹⁰ The 2-valent aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferably a saturated straight-chain or branched-chain aliphatic hydrocarbon group, and more preferably a saturated straight-chain aliphatic hydrocarbon group.

R ⁹ And R ¹⁰ The 2-valent aliphatic hydrocarbon groups represented may be the same or different, but are preferably the same.

The methylene group contained in the C1-20 aliphatic hydrocarbon group having a valence of 2 may be substituted by-O-. Examples of the group in which the methylene group contained in the 2-valent aliphatic hydrocarbon group is replaced with-O-, include groups represented by the following formulae. In the following formulae, the left-hand side indicates a bonding site to a nitrogen atom, and the right-hand side indicates a bonding site to an oxygen atom.

R ⁹ And R ¹⁰ The 2-valent aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by (a) may have a substituent, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group; -NR ^e R ^f (R ^e And R ^f Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; alkoxycarbonyl groups having 1 to 10 carbon atoms such as methoxycarbonyl and ethoxycarbonyl.

Wherein R is ⁹ And R ¹⁰ The 2-valent aliphatic hydrocarbon group is preferably a methylene group, an ethylene group, a propane-1, 3-diyl group or a butane-1, 4-diyl group.

As R ¹¹ And R ¹² Examples of the hydrocarbon group having 6 to 20 carbon atoms and having an aromatic hydrocarbon ring include a group having a bonding site in an aromatic hydrocarbon ring (hereinafter referred to as an aromatic hydrocarbon group), an aralkyl group having 7 to 20 carbon atoms, and the like. They may have a substituent.

Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and the like, and a benzene ring is preferable.

Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a tolyl group, a xylyl group, a dimethylethylphenyl group, a dimethylpropylphenyl group, a dimethylbutylphenyl group, a trimethylphenyl group, and a diisopropylphenyl group. Among them, aromatic hydrocarbon groups having an alkyl group at the ortho-position are preferable, and examples thereof include a2, 6-dimethylphenyl group, a2, 4, 6-trimethylphenyl group, a2, 6-diisopropylphenyl group, a2, 6-dimethyl-4-ethyl-phenyl group, a2, 6-dimethyl-4-propyl-phenyl group, a2, 6-dimethyl-4-butyl-phenyl group and the like. Further, if the alkyl group at the ortho position is bulky, there is a tendency that light resistance is excellent.

When the aromatic hydrocarbon group has a substituent, 1 or a plurality of the substituents may be present. When the aromatic hydrocarbon group has a plurality of substituents, the substituents may be the same or different. Examples of the substituent include a hydroxyl group; a carboxyl group; halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; a sulfamoyl group; c1-6 alkylsulfonyl such as methylsulfonyl; alkoxycarbonyl groups having 1 to 6 carbon atoms such as methoxycarbonyl and ethoxycarbonyl.

The hydrocarbon group having 6 to 20 carbon atoms and having an aromatic hydrocarbon ring may have a substituent such as a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, or the like, and preferably has a hydroxyl group.

When the above aromatic hydrocarbon group which may have a substituent has a methylene group, the methylene group may be substituted by-O-.

Examples of the aralkyl group having 7 to 20 carbon atoms include an aralkyl group in which an alkanediyl group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, and a propylene group is bonded to the aromatic hydrocarbon ring described in the above aromatic hydrocarbon group. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group, and a naphthylethyl group.

The aralkyl group having 7 to 20 carbon atoms may have a substituent, and when a plurality of the substituents are present, the substituents may be the same or different. The substituent may be bonded to the aromatic hydrocarbon ring or the alkanediyl group, and the substituent which may be bonded to the aromatic hydrocarbon ring is the same as the one described as the substituent of the aromatic hydrocarbon group.

When the aralkyl group having 7 to 20 carbon atoms which may have a substituent has a methylene group, the methylene group may be substituted by-O-.

R ¹¹ And R ¹² The hydrocarbon groups having 6 to 20 carbon atoms and having an aromatic hydrocarbon ring may be the same or different, and preferably the same.

Wherein R is ¹¹ And R ¹² The hydrocarbon group having 6 to 20 carbon atoms and having an aromatic hydrocarbon ring is preferably dimethylethylphenyl, dimethylpropylphenyl, dimethylbutylphenyl, dimethylmethoxyphenyl, dimethylethoxyphenyl or dimethylpropoxyphenyl, more preferably 2, 6-dimethyl-4-ethyl-phenyl, 2, 6-dimethyl-4-propyl-phenyl, 2, 6-dimethyl-4-butyl-phenyl, 2, 6-dimethyl-4-methoxy-phenyl, 2, 6-dimethyl-4-ethoxy-phenyl, 2, 6-dimethyl-4-propoxy-phenyl, still more preferably 2, 6-dimethyl-4-ethoxy-phenyl. Further, a substituent having a hydroxyl group as an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, or a propoxy group is preferable.

R ¹³ The saturated hydrocarbon group having 1 to 8 carbon atoms may be any of straight-chain, branched and cyclic. The saturated hydrocarbon group may be linear or branchedExamples thereof include methyl, ethyl, propyl, isobutyl, butyl, tert-butyl, hexyl, heptyl, octyl and the like. Examples of the cyclic saturated hydrocarbon group include a cyclopropyl group, a 1-methylcyclopropyl group, a cyclopentyl group, a cyclohexyl group, a1, 2-dimethylcyclohexyl group, and a cyclooctyl group.

Wherein R is ¹³ Particularly preferred is a hydrogen atom.

Examples of the compound (I) include compounds represented by the formulae (I-1) to (I-240) shown in tables 1 to 3.

[ Table 1]

[ Table 2]

[ Table 3]

In tables 1 to 3, A1-1 to A1-4 represent groups represented by the following formulae. In the following formulae, the left-hand side indicates a bonding site to a nitrogen atom, and the right-hand side indicates a bonding site to an oxygen atom.

In tables 1 to 3, A2-1 to A2-5 represent groups represented by the following formulae. In the following formulae, a represents a bonding site.

In addition, the compound (I) may include a compound represented by the following formula (II) (hereinafter, may be referred to as compound (II)) in addition to the compounds represented by the above formulae (I-1) to (I-240), and is preferably compound (II). The light resistance of the compound (II) is good.

[ in the formula (II),

R ¹ ～R ¹⁰ is represented by R in the formula (I) ¹ ～R ¹⁰ The same meaning is used.

X ¹ And X ² Each independently represents a hydrocarbon group having 1 to 14 carbon atoms having at least 1 group selected from a hydroxyl group and a carboxyl group, and a methylene group contained in the hydrocarbon group may be substituted by-O-.

R ¹⁴ And R ¹⁵ Each independently represents 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.

Wherein (X) ¹ ) _n1 And (R) ¹⁴ ) _5-n1 Total number of carbon atoms of (A) and (X) ² ) _n2 And (R) ¹⁵ ) _5-n2 The total number of carbon atoms of (2) is 14 or less.]

As X ¹ And X ² Examples of the hydrocarbon group having 1 to 14 carbon atoms include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof.

Examples of the linear aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.

Examples of the branched aliphatic hydrocarbon group include an isopropyl group, a sec-butyl group, a tert-butyl group, a methylpentyl group, an ethylpentyl group, a methylhexyl group, an ethylhexyl group, a propylhexyl group, and a tert-octyl group, and preferred examples thereof include an isopropyl group, a sec-butyl group, a tert-butyl group, and an ethylhexyl group.

Examples of the cyclic aliphatic hydrocarbon group include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, adamantyl, and the like.

Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumyl group, a mesityl group, a biphenyl group, a2, 6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group.

Examples of the group obtained by combining these include alkylcycloalkyl, cycloalkylalkyl, and aralkyl groups.

X ¹ And X ² The number of carbon atoms of the hydrocarbon group having 1 to 14 carbon atoms is preferably 1 to 10, more preferably 1 to 7, and still more preferably 1 to 4.

X ¹ And X ² The hydrocarbon group having 1 to 14 carbon atoms is preferably a linear or branched aliphatic hydrocarbon group, more preferably a linear aliphatic hydrocarbon group, and still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group.

X ¹ And X ² The hydrocarbon groups having 1 to 14 carbon atoms may be the same or different, but are preferably the same.

X ¹ And X ² Each independently preferably a hydrocarbon group having 1 to 10 carbon atoms and at least one group selected from a hydroxyl group and a carboxyl group,

X ¹ and X ² Each independently is more preferably a hydrocarbon group having 1 to 7 carbon atoms having at least one group selected from a hydroxyl group and a carboxyl group,

X ¹ and X ² Each independently of the other, is more preferably a hydrocarbon group having 1 to 4 carbon atoms and at least one group selected from a hydroxyl group and a carboxyl group,

X ¹ and X ² Each independently of the other, is more preferably a hydrocarbon group having 1 to 4 carbon atoms and a hydroxyl group.

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

As R ¹⁴ And R ¹⁵ Examples of the hydrocarbon group having 1 to 13 carbon atoms include the group X ¹ And X ² The same groups as those described for the hydrocarbon group having 1 to 14 carbon atoms.

R ¹⁴ And R ¹⁵ May be the same or different, but is preferablyAre the same.

Wherein R is ¹⁴ And R ¹⁵ Particularly preferred is a hydrogen atom.

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

(X ¹ ) _n1 And (R) ¹⁴ ) _5-n1 Total number of carbon atoms of (A) and (X) ² ) _n2 And (R) ¹⁵ ) _5-n2 The total number of carbon atoms of (2) is 14 or less. X ¹ 、X ² 、R ¹⁴ And R ¹⁵ When there are plural, each X ¹ 、X ² 、R ¹⁴ And R ¹⁵ May be the same or different, respectively.

The compound (II) includes compounds represented by the following formula (II-a), and specifically, compounds represented by the formulae (II-1) to (II-540) shown in tables 4 to 12, and the like.

[ Table 4]

[ Table 5]

[ Table 6]

[ Table 7]

[ Table 8]

[ Table 9]

[ Table 10]

[ Table 11]

[ Table 12]

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

In tables 4 to 12, A3-1 to A3-3 represent groups represented by the following formulae. In the following formulae, a indicates a bonding site.

In tables 4 to 12, A4-1 to A4-3 represent groups represented by the following formulae. In the following formulae, a represents a bonding site.

The compounds represented by the formulae (I), (II) and (II-a) each have preferably 2 to 10, more preferably 3 to 9, and further preferably 4 to 8 hydroxyl groups.

As the compound (I),

preferred are compounds represented by the formulae (I-1) to (I-180), the formulae (II-121) to (II-180), the formulae (II-331) to (II-375),

more preferably compounds represented by the formulae (I-25) to (I-36), the formulae (I-85) to (I-96), the formulae (I-145) to (I-156), the formulae (I-169) to (I-181), the formulae (II-121) to (II-150), the formulae (II-361) to (II-375),

further preferred are compounds represented by the formulae (II-133) to (II-135), and particularly preferred are compounds represented by the formula (II-135).

The compound represented by the formula (I) can be synthesized, for example, by the method described in Japanese patent laid-open No. 2020-055956.

The squarylium dye preferably contains a compound represented by the formula (III) (hereinafter, sometimes referred to as compound (III)). The compound (III) includes the resonance structure of the formula (III), and also includes a compound obtained by further rotating each group in the formula (III) or the resonance structural formula thereof around the bond axis of the carbon-carbon single bond or the carbon-nitrogen single bond.

[ in the formula (III),

R ³¹ ～R ³⁸ The alkyl group having 1 to 20 carbon atoms may beLinear, branched, and cyclic. Specific examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isobutyl group, a butyl group, a tert-butyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a heptadecyl group, and an undecyl group. Examples of the cyclic alkyl group include cyclopropyl, 1-methylcyclopropyl, cyclopentyl, cyclohexyl, 1, 2-dimethylcyclohexyl, cyclooctyl, 2,4, 6-trimethylcyclohexyl, and 4-cyclohexylcyclohexyl.

As R ³¹ ～R ³⁸ Examples of the substituent of the alkyl group having 1 to 20 carbon atoms include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like; a hydroxyl group; -NR ^k R ^l (R ^k And R ^l Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; alkoxy groups having 1 to 10 carbon atoms such as methoxy and ethoxy; alkoxycarbonyl groups having 1 to 10 carbon atoms such as methoxycarbonyl and ethoxycarbonyl.

As R ³¹ ～R ³⁸ The alkoxy group having 1 to 20 carbon atoms includes a group in which-O-is bonded to the bonding site of the alkyl group having 1 to 20 carbon atoms. Specific examples thereof include 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, and 2-ethylhexyloxy group.

As R ³¹ ～R ³⁸ The substituent of the alkoxy group having 1 to 20 carbon atoms includes a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.; a hydroxyl group; -NR ^m R ⁿ (R ^m And R ⁿ Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; alkoxy groups having 1 to 10 carbon atoms such as methoxy and ethoxy; alkoxycarbonyl groups having 1 to 10 carbon atoms such as methoxycarbonyl and ethoxycarbonyl.

R ³¹ ～R ³⁸ The alkyl group and alkoxy group having 1 to 20 carbon atoms preferably have 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 5 carbon atoms.

R ³¹ ～R ³⁸ R in (1) ³¹ ～R ³⁴ Particularly preferred is a hydrogen atom. In addition, R ³⁵ ～R ³⁸ Each independently of the other, is preferably a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms which may have a substituent, and more preferably a hydrogen atom or a hydroxyl group.

Preferably R ³¹ ～R ³⁸ (preferably R) ³⁵ ～R ³⁸ )2 to 4 of (a) are each independently a hydroxyl group, more preferably R ³¹ ～R ³⁸ (preferably R) ³⁵ ～R ³⁸ )2 to 3 of (a) are each independently a hydroxyl group, more preferably R ³¹ ～R ³⁸ (preferably R) ³⁵ ～R ³⁸ ) Each 2 of which is independently a hydroxyl group.

As R ³⁹ ～R ⁴² Examples of the hydrocarbon group having 1 to 20 carbon atoms 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, and is preferably saturated. The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear, branched or cyclic, and is preferably linear or branched.

Examples of the linear or branched aliphatic hydrocarbon having 1 to 20 carbon atoms include linear aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, vinyl, 1-propenyl, 2-propenyl (allyl), and the like; branched aliphatic hydrocarbon groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group. The aliphatic hydrocarbon group preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and further preferably 1 to 5 carbon atoms.

The cyclic aliphatic hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic aliphatic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. The number of carbon atoms of the cyclic aliphatic hydrocarbon group is preferably 3 to 8, more preferably 3 to 6.

The 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 a methylene group contained in the aliphatic hydrocarbon group is replaced with-O-include groups represented by the following formulae. In the following formulae, a represents a bonding site.

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

R ³⁹ ～R ⁴² The hydrocarbyl group having 1 to 20 carbon atoms represented by the formula (I) may have a substituent, and examples of the substituent include a carboxyl group; halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups having 1 to 10 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a sulfamoyl group; alkoxycarbonyl groups having 1 to 10 carbon atoms such as methoxycarbonyl and ethoxycarbonyl.

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

R ³⁹ ～R ⁴² At least one of the above groups 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, a bis (2, 2-dimethylphenyl group)Propyl) phenyl or; a phenyl group having 2 halogen atoms as a substituent, such as a2, 4-difluorophenyl group, a2, 4-dichlorophenyl group, a2, 4-dibromophenyl group, or a2, 4-diiodophenyl group, and more preferably a2, 4-dimethylphenyl group, a2, 4, 6-trimethylphenyl group, or a2, 4-difluorophenyl group.

In the compound (III), R is preferred ³⁹ And R ⁴² Each independently an aliphatic hydrocarbon group having 1 to 20 carbon atoms and having a carboxyl group as a substituent, R ⁴⁰ And R ⁴¹ Each independently an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms,

more preferably R ³⁹ And R ⁴² Each independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms and having a carboxyl group as a substituent, R ⁴⁰ And R ⁴¹ Each independently an optionally substituted aromatic hydrocarbon group having 6 to 16 carbon atoms,

further preferred is R ³⁹ And R ⁴² Each independently is an aliphatic hydrocarbon group having 1 to 8 carbon atoms and having a carboxyl group as a substituent, R ⁴⁰ And R ⁴¹ Each independently an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms,

further preferred is R ³⁹ And R ⁴² Each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms and having a carboxyl group as a substituent, R ⁴⁰ And R ⁴¹ Each independently an optionally substituted aromatic hydrocarbon group having 6 to 9 carbon atoms.

The compound (III) preferably has 2 to 4 hydroxyl groups and 2 to 4 carboxyl groups, more preferably has 2 to 3 hydroxyl groups and 2 to 3 carboxyl groups, and further preferably has 2 hydroxyl groups and 2 carboxyl groups.

Examples of the compound (III) include compounds represented by the formulae (III-1) to (III-180) shown in tables 13 to 15.

The compound (III) is preferably a compound represented by any one of the formulae (III-1) to (III-90) and (III-121) to (III-180), more preferably a compound represented by any one of the formulae (III-1) to (III-30) and (III-121) to (III-150), still more preferably a compound represented by any one of the formulae (III-1) to (III-3), formulae (III-19) to (III-21) and formulae (III-127) to (III-129), still more preferably a compound represented by any one of the formulae (III-1) to (III-3), and particularly preferably a compound represented by any one of the formulae (III-3).

[ Table 13]

[ Table 14]

[ Table 15]

In tables 13 to 15, ph1 to ph10 represent groups represented by the following formulae (indicates bonding sites).

In tables 13 to 15, ca1 to ca6 represent groups represented by the following formulae (a indicates a bonding site).

The compound represented by the formula (III) can be synthesized, for example, by the method described in Japanese patent laid-open publication No. 2019-163233.

The squarylium dye preferably contains at least 1 selected from the group consisting of the compound (I) and the compound (III).

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

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

The amount of the squarylium dye is 3 to 140 parts by mass, more preferably 5 to 130 parts by mass, and still more preferably 10 to 120 parts by mass, based on 100 parts by mass of the polymerization initiator (D). When the ratio is within the above range, a color filter having a good contrast can be obtained.

When the squarylium dye is the compound (I) (including the compound (II)), the content of the compound (I) is preferably 3 to 140 parts by mass, more preferably 18 to 135 parts by mass, still more preferably 50 to 130 parts by mass, and yet more preferably 90 to 125 parts by mass, based on 100 parts by mass of the polymerization initiator (D). When the squarylium dye is the compound (I), the following tendency is exhibited: the higher the content of the compound (I) relative to the polymerization initiator (D), the higher the contrast.

When the squarylium dye is the compound (III), the content of the compound (III) is preferably 3 to 140 parts by mass, more preferably 18 to 135 parts by mass, still more preferably 50 to 130 parts by mass, and yet more preferably 90 to 125 parts by mass, based on 100 parts by mass of the polymerization initiator (D). When the squarylium dye is the compound (III), the following tendency is exhibited: the higher the content of the compound (III) relative to the polymerization initiator (D), the higher the contrast.

The colorant (a) may contain a colorant different from the compound (I) and the compound (III) in addition to the compound (I) and the compound (III). The colorant different from the compound (I) and the compound (III) may be any of a dye (hereinafter, sometimes referred to as a dye (a1)) and a pigment (hereinafter, sometimes referred to as a pigment (a 2)). A colorant different from compound (I) and compound (III) may contain one or both of these dye (a1) and pigment (a 2).

As the dye (a1), any known dye may be used without particular limitation as long as it does not contain the compound (I) or the compound (III), and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. As The dye, for example, there can be mentioned a dye classified into other than pigments in The color index (published by The Society of Dyers and Colourists)Compounds other than those having a color tone, and known dyes described in dyeing guidelines (available from color dyeing Co.). Further, depending on the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, azo dyes, and the like,

Xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes (wherein compounds (I) and (III) are excluded), acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, and the like. Among them, organic solvent-soluble dyes are preferable.

Specifically, c.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, 59:1, 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. solvent dyes such as c.i. solvent green 1,3, 4,5, 7, 28, 29, 32, 33, 34, 35;

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, 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, 90:1, 91, 92, 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, 243, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 267, 256, 259, 280, 278, 296, 285, 315, 324, 285, 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: 1. 58, 63, 65, 80, 104, 105, 106, 109, and the like c.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, 244, 246, 247, 245, 250, 251, 252, 257, 275, 268, 293, 268, 248;

c.i. direct dyes such as c.i. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;

c.i. disperse yellow 51, 54, 76;

c.i. disperse violet 26, 27;

c.i. disperse dyes such as c.i. disperse blue 1,14, 56, 60, etc.;

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 dyes such as c.i. basic green 1;

c.i. reactive yellow 2, 76, 116;

c.i. reactive orange 16;

c.i. reactive dyes such as c.i. reactive red 36;

c.i. media yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

c.i. medium red 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. intermediate 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. media 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. medium 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. mediator dyes such as c.i. mediator green 1,3, 4,5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53;

c.i. vat dyes such as c.i. vat green 1, and the like.

These dyes may be appropriately selected so as to match the spectral spectrum of a desired color filter.

As The pigment (a2), known pigments can be used without particular limitation, and examples thereof include pigments classified as pigments (pigments) in The color index (published by The Society of Dyers and Colourists).

Examples of the pigment include yellow pigments such as c.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, 147, 148, 150, 153, 154, 166, 173, 194, 214;

orange pigments such as c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

red pigments such as c.i. 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. pigment blue 15, 15:3, 15:4, 15:6, 60, etc.;

c.i. pigment violet 1, 19, 23, 29, 32, 36, 38 and the like violet pigment;

green pigments such as c.i. pigment green 7, 36, 58;

c.i. brown pigments such as pigment brown 23, 25;

and black pigments such as c.i. pigment black 1 and 7.

The pigment may be subjected to rosin treatment, surface treatment using a pigment derivative or the like into which an acidic group or a basic group has been introduced, grafting treatment of the pigment surface with a polymer compound or the like, micronization treatment by a sulfuric acid micronization method or the like, cleaning treatment by an organic solvent, water or the like for removing impurities, removal treatment by an ion exchange method or the like for removing ionic impurities, or the like, as necessary.

The pigment is preferably uniform in particle size. The pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained by performing the dispersion treatment with the pigment dispersant.

Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamide, and acrylic surfactants. These pigment dispersants may be used alone or in combination of 2 or more. Examples of the pigment dispersant include KP (manufactured by shin-Etsu chemical Co., Ltd.), FLOWLEN (manufactured by Kyoho chemical Co., Ltd.), Solsperse (manufactured by Zeneca), EFKA (manufactured by CIBA Co., Ltd.), AJISPER (manufactured by Ajinko chemical Co., Ltd.), Disperbyk (manufactured by BYK Co., Ltd.) and the like.

When a pigment dispersant is used, the amount thereof to be used is preferably 1 to 100% by mass, more preferably 5 to 50% by mass, based on the total amount of the pigment (a 2). When the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.

The content of the colorant (a) in the colored curable resin composition is preferably 0.1 to 70% by mass, more preferably 0.5 to 60% by mass, and still more preferably 1 to 50% by mass, based on the total amount of solid components.

The content of the squarylium dye in the colored curable resin composition is preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass, and still more preferably 1 to 20% by mass, based on the total amount of solid components.

When the content of the colorant (a) and the squarylium dye is within the above range, the color density in the formation of a color filter is sufficient, and the desired amounts of the resin (B) and the polymerizable compound (C) can be contained in the composition, so that a pattern having sufficient mechanical strength can be formed.

Here, the "total amount of solid components" in the present specification means an amount obtained by removing the content of the solvent from the total amount of the colored curable resin composition. The total amount of the solid components and the contents of the respective components relative to the total amount can be measured by a known analytical means such as liquid chromatography or gas chromatography.

< resin (B) >

The resin (B) is preferably an alkali-soluble resin, and more preferably a polymer having a structural unit derived from at least 1 monomer (hereinafter, sometimes referred to as "monomer (a)") selected from an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride.

The resin (B) is preferably a copolymer having a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (B)") and other structural units.

Examples of the other structural units include structural units derived from a monomer copolymerizable with the monomer (a) (which is different from the monomer (a) and the monomer (b): hereinafter, sometimes referred to as "monomer (c)"), structural units having an ethylenically unsaturated bond, and the like.

In the present specification, "(meth) acrylic acid" means at least 1 selected from acrylic acid and methacrylic acid. The same meanings are also given to "(meth) acryloyl group" and "(meth) acrylate" and the like.

Examples of the monomer (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, and p-vinylbenzoic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5, 6-tetrahydrophthalic acid, 1,2,3, 6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1, 4-cyclohexene dicarboxylic acid; carboxyl group-containing bicyclic unsaturated compounds such as 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; unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride; unsaturated mono [ (meth) acryloyloxyalkyl ] esters of 2-or more-membered polycarboxylic acids such as succinic acid mono [ 2- (meth) acryloyloxyethyl ester ] and phthalic acid mono [ 2- (meth) acryloyloxyethyl ester ]; and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as α - (hydroxymethyl) acrylic acid.

Among them, acrylic acid, methacrylic acid, o-, m-, p-vinylbenzoic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and solubility of the obtained resin in an aqueous alkali solution.

The monomer (b) is a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least 1 selected from an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (an oxetane ring)) and an ethylenically unsaturated bond.

The monomer (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

Examples of the monomer (b) include a monomer having an oxetanyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (b 1)"), a monomer having an oxetanyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (b 2)"), a monomer having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (b 3)"), and the like.

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

As the monomer (b 1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable.

Examples of the monomer (b 1-1) include glycidyl (meth) acrylate, β -methylglycidyl (meth) acrylate, β -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α -methyl-o-vinylbenzyl glycidyl ether, α -methyl-m-vinylbenzyl glycidyl ether, α -methyl-p-vinylbenzyl glycidyl ether, 2, 3-bis (glycidoxymethyl) styrene, 2, 4-bis (glycidoxymethyl) styrene, 2, 5-bis (glycidoxymethyl) styrene, 2, 6-bis (glycidoxymethyl) styrene, 2,3, 4-tris (glycidoxymethyl) styrene, 2,3, 5-tris (glycidoxymethyl) styrene, 2,3, 6-tris (glycidoxymethyl) styrene, 3,4, 5-tris (glycidoxymethyl) styrene, 2,4, 6-tris (glycidoxymethyl) styrene and the like.

Examples of the monomer (b 1-2) include vinylcyclohexene monooxide, 1, 2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000 (manufactured by Daicel Co., Ltd.), (3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer (registered trademark) A400 (manufactured by Daicel Co., Ltd.), (3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer (registered trademark) M100 (manufactured by Daicel Co., Ltd.)), the compound represented by the formula (BI), and the compound represented by the formula (BII).

[ formula (BI) and formula (BII) wherein R ^a And R ^b Independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group.

X ^a And X ^b Independently of one another, represents 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.

Denotes the bonding site to O. ]

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

Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.

As R ^a And R ^b Preferred examples thereof include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferred examples thereof include a hydrogen atom and a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1, 2-diyl group, a propane-1, 3-diyl group, a butane-1, 4-diyl group, a pentane-1, 5-diyl group, and a hexane-1, 6-diyl group.

As X ^a And X ^b Preferred examples thereof include a single bond, methylene, ethylene and-CH ₂ －O－、*－CH ₂ CH ₂ More preferably, the group-O-includes a single bond and-CH ₂ CH ₂ -O- (. indicates a bonding site to O).

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

The compound represented by the formula (BII) includes compounds represented by any one of the formulae (BII-1) to (BII-15), and the like, and among them, compounds represented by the formulae (BII-1), (BII-3), (BII-5), (BII-7), the formula (BII-9), and the formulae (BII-11) to (BII-15) are preferable, and compounds represented by the formulae (BII-1), (BII-7), the formula (BII-9), and the formula (BII-15) are more preferable.

The compound represented by the formula (BI) and the compound represented by the formula (BII) may be used alone or in combination of 2 or more. It is also possible to use the compound represented by the formula (BI) in combination with the compound represented by the formula (BII). When the compound represented by the formula (BI) and the compound represented by the formula (BII) are used in combination, the content ratio [ the compound represented by the formula (BI): the compound represented by the formula (BII) ] is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and further preferably 20:80 to 80:20 on a molar basis.

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 preferable.

Examples of the monomer (b2) include 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, 3-methyl-3- (meth) acryloyloxyethyloxyoxetane, and 3-ethyl-3- (meth) acryloyloxyethyloxyoxetane.

As the monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuranyl group and a (meth) acryloyloxy group is more preferable.

Examples of the monomer (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V #150, manufactured by Osaka Organischen chemical industries, Ltd.), tetrahydrofurfuryl methacrylate, and the like.

The monomer (b) is preferably the monomer (b1) in view of enabling the obtained color filter to have higher reliability such as heat resistance, chemical resistance and the like. Further, the monomer (b 1-2) 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, and tricyclo [5.2.1.0 ] meth) acrylate ² ^,6 ]Decan-8-yl ester (which is known as "dicyclopentyl (meth) acrylate" as a common name in the art, and may be referred to as "tricyclodecyl (meth) acrylate" in some cases), and tricyclo (meth) acrylate [5.2.1.0 ^2,6 ]Decan-9-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid) ^2,6 ]Decen-8-yl ester (commonly known in the art as "dicyclopentenyl (meth) acrylate"), (meth) acrylic acid tricyclo [5.2.1.0 ] ^2,6 ]Decen-9-yl ester, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, and (meth) acrylic acidBenzyl esters and the like (meth) acrylates;

hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

halogen atom-containing (meth) acrylates 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-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-bis (2' -hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-dimethoxybicyclo [ 2.1] hept-2-ene, 5, 6-bis (2.1) hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxyhept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-2.1 ] hept-2-ene, 5-hydroxy-2-hydroxy-2-hydroxy-1-2-hydroxy-2-1-hydroxy-2-hydroxy-2-1-2-ethyl-2-ene, 5-hydroxy-2-hydroxy-2, 5, 6-2-hydroxy-2-one, 5-2-one, 5, 6-one, 2-one, 2-one, 5, Bicyclic unsaturated compounds such as 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonybicyclo [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 (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;

dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-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 chloride 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.

Among them, styrene, vinyltoluene, and tricyclo [5.2.1.0 ] meth (acrylic acid) are preferable from the viewpoint of copolymerization reactivity and heat resistance ^2,6 ]Decan-8-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid) ^2,6 ]Decan-9-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid) ^2,6 ]Decen-8-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid) ^2,6 ]Decen-9-yl ester, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1]Hept-2-ene, phenyl (meth) acrylate, 2,3,3,4,4,5, 5-octafluoropentyl (meth) acrylate, 9-vinylcarbazole, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.

Specific examples of the resin (B) include a3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid copolymer, and a3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid) ^2,6 ]Decyl ester/(meth) acrylic acid copolymer, 3, 4-epoxy tricyclo [5.2.1.0 ] meth (acrylic acid) ^2,6 ]Decyl ester/(benzyl (meth) acrylate/(meth) acrylic acid copolymer, 3, 4-epoxy tricyclo [5.2.1.0 ] meth (acrylic acid) ^2,6 ]Decyl ester/9-vinyl carbazole/(meth) acrylic acid copolymer, and (meth) acrylic acid 3, 4-epoxy tricyclo [5.2.1.0 ^2,6 ]Decyl ester/(methyl) acrylic acid phenyl ester/o-vinylbenzoic acid copolymer, and 3, 4-epoxy tricyclo [5.2.1.0 ] of (methyl) acrylic acid ^2,6 ]Decyl ester/(methyl) acrylic acid phenyl ester/m-vinyl benzoic acid copolymer, and 3, 4-epoxy tricyclo [5.2.1.0 ] of (methyl) acrylic acid ^2,6 ]Decyl ester/(methyl) acrylic acid phenyl ester/p-vinyl benzoic acid copolymer, and 3, 4-epoxy tricyclo [5.2.1.0 ] of (methyl) acrylic acid ^2,6 ]Decyl ester/(methyl) acrylic acid phenyl ester/(methyl) acrylic acid copolymer, and 3, 4-epoxy tricyclo [5.2.1.0 ] of (methyl) acrylic acid ^2,6 ]Decyl ester/(meth) acrylic acid 2,2,3,3,4,4,5, 5-octafluoropentyl ester/(meth) acrylic acid copolymer, glycidyl (meth) acrylate/(meth) acrylic acid benzyl ester/(meth) acrylic acid copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid) ^2,6 ]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, 3, 4-epoxy tricyclo [5.2.1.0 ] of (meth) acrylic acid ^2,6 ]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid) ^2,6 ]Decyl ester/(meth) acrylic acid/vinyltoluene copolymer, 3, 4-epoxy tricyclo [5.2.1.0 ] acrylic acid ^2,6 ]Decyl ester/(meth) acrylic acid 2-ethylhexyl ester copolymer, 3, 4-epoxy tricyclo [5.2.1.0 ] meth (acrylic acid) ^2,6 ]Decyl ester/(meth) acrylic acid tricyclo [5.2.1.0 ² ^,6 ]Decenyl ester/(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 copolymer, and resins described in each of Japanese patent application laid-open Nos. 9-106071, 2004-29518 and 2004-361455.

Among these, the resin (B) is preferably a copolymer containing a structural unit derived from the monomer (a) and a structural unit derived from the monomer (B).

The resin (B) may be combined with 2 or more, in which case the resin (B) preferably contains at least 1 copolymer containing a structural unit derived from the monomer (a) and a structural unit derived from the monomer (B), more preferably contains at least 1 copolymer containing a structural unit derived from the monomer (a) and a structural unit derived from the monomer (B1), further preferably contains at least 1 copolymer containing a structural unit derived from the monomer (a) and a structural unit derived from the monomer (B1-2), and further preferably contains at least 1 copolymer selected from 3, 4-epoxytricyclo [5.2.1.0 ] of (meth) acrylic acid ^2,6 ]Decyl ester/(methyl) acrylic acid copolymer, and (methyl) acrylic acid 3, 4-epoxy tri-compoundCyclo [5.2.1.0 ^2,6 ]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid) ^2,6 ]Decyl ester/(meth) acrylic acid/vinyltoluene copolymer, 3, 4-epoxy tricyclo [5.2.1.0 ] of (meth) acrylic acid ^2,6 ]1 or more of decyl ester/(meth) acrylic acid 2-ethylhexyl ester copolymer.

The weight average molecular weight (Mw) of the resin (B) in terms of polystyrene is preferably 1000 to 100000, more preferably 2000 to 50000, still more preferably 3000 to 30000, and still more preferably 5000 to 30000. When the weight average molecular weight is within the above range, the unexposed portion tends to have high solubility in a developer, and the resulting pattern tends to have a high residual film ratio and high hardness.

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

The acid value (solid content equivalent value) of the resin (B) is preferably from 10 mg-KOH/g to 300 mg-KOH/g, more preferably from 20 mg-KOH/g to 250 mg-KOH/g, still more preferably from 25 mg-KOH/g to 200 mg-KOH/g, yet more preferably from 30 mg-KOH/g to 180 mg-KOH/g, and particularly preferably from 40 mg-KOH/g to 150 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1g of the resin, and can be determined by titration using 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, even more preferably 13 to 70% by mass, and even more preferably 15 to 60% by mass, based on 100% by mass of the solid content of the colored curable resin composition. When the content of the resin (B) is within the above range, the unexposed portion tends to have high solubility in a developer.

< polymerizable Compound (C) >

The polymerizable compound (C) is a compound which can be polymerized by an active radical and/or an acid generated by the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and preferably (meth) acrylate compounds.

The average number of equivalents of ethylenically unsaturated groups of the polymerizable compound (C) is less than 96.0. The present inventors have conducted studies and, as a result, have found that when the average number of equivalents of ethylenically unsaturated groups exceeds the above range, the contrast of the color filter deteriorates.

The average number of equivalents of ethylenically unsaturated groups in the polymerizable compound (C) is preferably 95.5 or less, more preferably 95.0 or less, still more preferably 94.5 or less, and still more preferably 94.0 or less. The lower limit is not particularly limited, and the average number of equivalents of ethylenically unsaturated groups in the polymerizable compound (C) is preferably 83.0 or more, more preferably 83.5 or more, still more preferably 84.0 or more, still more preferably 84.5 or more, and particularly preferably 85.0 or more.

The average number of equivalents of ethylenically unsaturated groups in the polymerizable compound (C) is calculated from formula (1).

< average number of equivalents of ethylenically unsaturated group >

The average number of equivalents of ethylenically unsaturated groups of the polymerizable compound (C) is represented by formula (1).

[ in the formula (1),

m _i Represents the mole fraction of the component i.]

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 may be used as long as the average number of equivalents of ethylenically unsaturated groups of the polymerizable compound (C) is less than 96.0. Examples of the polymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, and mixtures thereof, 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 1 selected from pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and glycerol tri (meth) acrylate, and more preferably contains at least 1 selected from pentaerythritol triacrylate, pentaerythritol tetraacrylate, and glycerol triacrylate.

The polymerizable compound (C) may be a combination of 2 or more of the above-mentioned exemplified compounds, or 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) to pentaerythritol tetra (meth) acrylate (y) is preferably 1 to 99 mol%, more preferably 10 to 90 mol%, 90 to 10 mol%, further preferably 20 to 80 mol%, 80 to 20 mol%, further preferably 30 to 70 mol%, and 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, even more preferably 10 to 55% by mass, and even more preferably 15% by mass or more, 20% by mass or more, or 25% by mass or more, based on the total amount of the solid content. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming a colored pattern and the chemical resistance of the color filter tend to be improved. In addition, if the content ratio 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 generating an active radical, an acid, or the like under the action of light or heat to initiate polymerization, and a known polymerization initiator can be used. As the polymerization initiator generating active radicals, for example, an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a bisimidazole compound can be cited.

Examples of the O-acyloxime compounds include O-acyloxime compounds having a diphenyl sulfide skeleton such as N-benzoyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine, N-benzoyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine, N-benzoyloxy-1- (4-phenylthiophenyl) -3-cyclopentylpropane-1-one-2-imine, and N-acetoxy-1- (4-phenylthiophenyl) -3-cyclohexylpropane-1-one-2-imine; o-acyloxime compounds having a carbazole skeleton such as N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- { 2-methyl-4- (3, 3-dimethyl-2, 4-dioxopentylmethoxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-one-2-imine; and O-acyloxime compounds having a fluorene skeleton such as 1- [ 7- (2-methylbenzoyl) -9, 9-dipropyl-9H-fluoren-2-yl ] ethanone O-acetyloxime. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (both of which are available from BASF corporation), PBG-327 (available from Changzhou powerful electronic New Material Co., Ltd.), N-1919 (available from ADEKA corporation), and DFI-091 (available from DAITO CHEMIX Co., Ltd.) can also be used. Among them, the O-acyloxime compound is preferably at least 1 selected from the group consisting of N-benzoyloxy-1- (4-phenylthiophenyl) octan-1-one-2-imine, N-acetoxy-1- (4-phenylthiophenyl) -3-cyclohexylpropane-1-one-2-imine, N-acetoxy-1- [ 9-ethyl-6- { 2-methyl-4- (3, 3-dimethyl-2, 4-dioxopentylmethoxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine and 1- [ 7- (2-methylbenzoyl) -9, 9-dipropyl-9H-fluoren-2-yl ] ethanone O-acetyloxime. In the case of these O-acyloxime compounds, color filters having high luminance tend to be obtained.

Examples of the above-mentioned alkylphenone compounds include 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [ 4- (4-morpholino) 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, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone, benzildimethylketal, and the like. Commercially available products such as Irgacure (registered trademark) 369, 907, and 379 (both manufactured by BASF corporation) may 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-methoxystyryl) -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (5-methylfuran-2-yl) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (furan-2-yl) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (4-diethylamino-2-methylphenyl) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (3, 4-dimethoxyphenyl) vinyl ] -1, 3, 5-triazine and the like.

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

Examples of the biimidazole compound include 2,2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenylbiimidazole, 2' -bis (2, 3-dichlorophenyl) -4, 4 ', 5, 5' -tetraphenylbiimidazole (see, for example, japanese unexamined patent publication No. 6-75372, japanese unexamined patent publication No. 6-75373, etc.), 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenylbiimidazole, 2' -bis (2-chlorophenyl) -4, 4 ', 5, 5' -tetrakis (alkoxyphenyl) biimidazole, 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetrakis (dialkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4, 4 ', 5, 5' -tetrakis (trialkoxyphenyl) biimidazole (for example, see, for example, JP-B-48-38403 and JP-A-62-174204), and biimidazole compounds in which the phenyl group at the 4,4 ', 5, 5' -position is substituted with a carboalkoxy group (see, for example, JP-A-7-10913).

Examples of the polymerization initiator generating an acid include onium salts such as 4-hydroxyphenyl dimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyl dimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyl dimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate and diphenyliodonium hexafluoroantimonate, nitrobenzyl toluenesulfonate and benzoin toluenesulfonate.

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone; quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl benzoylformate, titanocene compounds, and the like.

As the polymerization initiator (D), a polymerization initiator containing at least 1 selected from the group consisting of an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a bisimidazole compound is preferable, and a polymerization initiator containing an O-acyloxime compound is more preferable.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 25 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be high and the exposure time tends to be short, so that the productivity of the color filter tends to be improved.

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, and yet more preferably 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 with respect to 100 parts by mass of the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, the contrast tends to be improved, and when the content is smaller 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, even more preferably 1 to 20% by mass, and even more preferably 15% by mass or less or 10% by mass, based on the total amount of the solid content. When the content of the polymerization initiator (D) is within the above range, the contrast tends to be improved, and when the content is smaller within the above range, the contrast tends to be further improved.

< polymerization initiation aid (D1) >

The polymerization initiation aid (D1) is a compound or sensitizer for promoting the polymerization of a polymerizable compound whose polymerization is initiated by a polymerization initiator. When the polymerization initiation aid (D1) is contained, 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, 2-ethylhexyl 4-dimethylaminobenzoate, N-dimethyl-p-toluidine, 4 '-bis (dimethylamino) benzophenone (commonly known as michelson), 4' -bis (diethylamino) benzophenone, and 4,4 '-bis (ethylmethylamino) benzophenone, and among them, 4' -bis (diethylamino) benzophenone is preferable. Commercially available products such as EAB-F (manufactured by Baotu chemical industries, Ltd.) may also be used.

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

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

Examples of the carboxylic acid compound include phenylthioglycolic acid, methylphenylthioacetic acid, ethylphenylthioglycolic acid, methylethylphenylthioglycolic acid, dimethylphenylthioacetic acid, methoxyphenylthioglycolic acid, dimethoxyphenylthioglycolic acid, chlorophenylthioglycolic acid, dichlorophenylthioglycolic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioglycolic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

When the polymerization initiator aid (D1) is used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). 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 the color filter tends to be improved.

< solvent (E) >

The solvent (E) is not particularly limited, and a solvent generally used in this field can be used. Examples thereof include an ester solvent (a solvent containing-COO-and not containing-O-in the molecule), an ether solvent (a solvent containing-O-and not containing-COO-in the molecule), an ether ester solvent (a solvent containing-COO-and-O-in the molecule), a ketone solvent (a solvent containing-CO-and not containing-COO-in the molecule), an alcohol solvent (a solvent containing OH and not containing-O-, -CO-, and-COO-, an aromatic hydrocarbon solvent, an amide solvent, and dimethyl sulfoxide.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ -butyrolactone.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1, 4-dibutylbutanol, tetrahydrofuran, and the like

Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 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 monoethylether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, diethylene glycol monobutyl ether acetate, and the like.

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

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

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

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

Among the above solvents, organic solvents having a boiling point of 120 to 180 ℃ at 1atm are preferable from the viewpoint of coatability and drying property. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, and N, N-dimethylformamide are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethyl lactate, and ethyl 3-ethoxypropionate are more preferable.

The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention. In other words, the total content of the solid content in the colored curable resin composition is preferably 5 to 30% by mass, and 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 becomes good, and the color density is not insufficient at the time of forming a color filter, so that the display characteristics tend to become good.

< leveling agent (F) >

Examples of the leveling agent (F) include a silicone surfactant, a fluorine surfactant, and a silicone surfactant having a fluorine atom. These may have a polymerizable group in a side chain.

Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Dow Corning Toray 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 Moviive Performance Properties Japan contract Co., Ltd.), and the like can be cited.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, examples thereof include FLUORAD (registered trademark) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC (Co., Ltd.), F-top (registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi electro chemical Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by AGC (Co., Ltd.) and E5844 (manufactured by Sangon chemical Co., Ltd.).

Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, there may be mentioned MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477 and MEGAFAC F443 (manufactured by DIC Co., Ltd.).

The content of the leveling agent (F) is preferably 0.001 to 0.2% by mass, more preferably 0.002 to 0.2% by mass, and still more preferably 0.005 to 0.2% by mass, based on the total amount of the colored curable resin composition. The content of the dispersant is not included in the content. 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 contain additives known in the art, such as a polymerization initiation aid, a filler, another polymer compound, an adhesion promoter, a light stabilizer, and a chain transfer agent, as necessary.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-isocyanatoethyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-methyldimethoxysilane, 3-methacryloxysilane, 3-2-methacryloxysilane, 3-isocyanatoethylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-3-aminopropyltrimethoxysilane, and the like, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane and the like.

< method for producing colored curable resin composition >

The colored curable resin composition can be prepared, for example, by mixing the colorant (a), the resin (B), the polymerizable compound (C), the polymerization initiator (D), and if necessary, the solvent (E), the leveling agent (F), the polymerization initiation aid (D1), and other components.

The colorant (a) may be contained in the pigment dispersion liquid in advance. The target colored curable resin composition can be prepared by mixing the remaining components into the pigment dispersion liquid so as to reach a predetermined concentration.

The dye in the case of containing the dye may be dissolved in a part or the whole of the solvent (E) in advance to prepare a solution. Preferably, the solution is filtered through a filter having a pore size of about 0.01 to 1 μm.

The mixed colored curable resin composition is preferably filtered through a filter having a pore diameter 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 photolithography, an ink jet method, and a printing method. Among them, photolithography is preferable. The photolithography method is a method in which the colored curable resin composition is applied to a substrate and dried to form a composition layer, and the composition layer is exposed to light through a photomask and developed. In the photolithography method, a colored coating film which is a cured product of the composition layer can be formed without using a photomask and/or without performing development at the time of exposure.

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, further preferably 3 μm or less, further preferably 1.5 μm or less, particularly preferably 0.5 μm or less, preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more.

As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass having a silica-coated surface, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, a substrate of silicon, a substrate having a thin film of aluminum, silver/copper/palladium alloy formed on the substrate, or the like can be used. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates. In addition, a substrate subjected to HMDS treatment on a silicon substrate may be used.

The formation of each colored pixel by photolithography can be performed by a known or conventional apparatus and conditions. For example, the following can be used. First, a colored curable resin composition is applied onto a substrate, and is dried by heating (prebaking) and/or drying under reduced pressure to remove volatile components such as a solvent and to obtain a smooth composition layer. Examples of the coating method include a spin coating method, a slit coating method, and a slit spin coating method. The temperature for the heat drying is preferably 30 to 120 ℃, more preferably 50 to 110 ℃. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. When the drying is carried out under reduced pressure, the drying is preferably carried out under a pressure of 50 to 150Pa and at a temperature of 20 to 25 ℃. The film thickness of the composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

Next, the composition layer is exposed through a photomask for forming a target colored pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the intended use is used. The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350nm may be cut off using a filter that cuts off the wavelength region, or light near 436nm, near 408nm, or near 365nm may be selectively extracted using a band-pass filter that extracts these wavelength regions. Specifically, mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like can be given. In order to uniformly irradiate parallel light to the entire exposure surface and perform precise alignment of the photomask and the substrate, a reduction projection exposure apparatus or a proximity exposure apparatus such as a mask aligner and a stepper is preferably used.

The exposed composition layer is brought into contact with a developer to develop the composition layer, thereby forming a colored pattern on the substrate. The unexposed portion of the composition layer is dissolved in a developing solution and removed by development. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. The developer may contain a surfactant. The developing method may be any of a spin-coating immersion method, a dipping method, a spraying method, and the like. Further, the substrate can be inclined at an arbitrary angle during development.

After development, washing with water is preferred.

Further, the obtained colored pattern is preferably subjected to post-baking. The postbaking temperature is preferably from 80 ℃ to 250 ℃ and more preferably from 100 ℃ to 245 ℃. The post-baking time is preferably 1 minute to 120 minutes, more preferably 2 minutes to 30 minutes.

The colored pattern and the colored coating film obtained by the above method are useful as a color filter, and the color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, or the like), electronic paper, a solid-state imaging device, or the like.

Examples

The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In the examples,% and parts indicating the content or amount used are by mass unless otherwise specified.

[ Synthesis example 1]

The compound represented by the formula (II-135) was obtained in accordance with example 8 described in Japanese patent laid-open No. 2020-055956.

[ Synthesis example 2]

A compound represented by the formula (III-3) was obtained in accordance with example 2 described in Japanese patent application laid-open No. 2019-163233.

[ resin Synthesis example 1]

An appropriate amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the atmosphere was changed to nitrogen, and 280 parts of propylene glycol monomethyl ether acetate was added and heated to 80 ℃ with stirring. Then, 38 parts of acrylic acid and 3, 4-epoxytricyclo [5.2.1.0 ] acrylic acid were added dropwise over 5 hours ^2,6 ]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0 ² ^,6 ]Process for preparing decan-9-yl estersA mixed solution of 289 parts of the mixture (containing 1:1 parts by mole) and 125 parts of propylene glycol monomethyl ether acetate. 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 completion of the dropwise addition, the flask was kept at 80 ℃ for 4 hours, and then cooled to room temperature to obtain a copolymer (resin (B-1)) solution having a B-type viscosity (23 ℃) of 125 mPas and a solid content of 35.1%. The weight-average molecular weight Mw of the resulting copolymer was 9200, the dispersity was 2.08, and the acid value of the solid portion was 77 mg-KOH/g.

The resin (B-1) has the following structural unit.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin in terms of polystyrene were measured by GPC under the following conditions.

A device; HLC-8120 GPC (manufactured by Tosoh corporation)

A column; TSK-GELG 2000HXL

Column temperature; 40 deg.C

A solvent; THF (tetrahydrofuran)

A flow rate; 1.0mL/min

Detecting the concentration of the solid component in the liquid; 0.001 to 0.01% by mass

Sample size; 50 μ L

A detector; RI (Ri)

A calibration standard substance; TSKSTANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh corporation)

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

Examples 1 to 24 and comparative example 1

[ preparation of colored curable resin composition ]

The respective components were mixed so as to have the compositions shown in tables 16 to 17, thereby obtaining colored curable resin compositions.

In tables 16 to 17, each component represents the following compounds.

Colorant (A-1): a compound represented by the formula (II-135)

Colorant (a-2): a compound represented by the formula (III-3)

Resin (B-1): resin (B-1) (conversion of solid content)

Polymerizable compound (C-1): pentaerythritol tetraacrylate (average number of equivalents of ethylenically unsaturated groups 88.1; A-TMMT; manufactured by Newzhongcun chemical industry Co., Ltd.)

Polymerizable compound (C-2): pentaerythritol triacrylate and pentaerythritol tetraacrylate (average number of equivalents of ethylenically unsaturated groups 94.6; A-TMM-3 LM-N; about 57 mol% for 3 functional group, about 43 mol% for 4 functional group; manufactured by Ningzhou chemical industry Co., Ltd.)

Polymerizable compound (C-3): glycerol triacrylate (average ethylenically unsaturated group equivalent: 84.7; ARONIX (registered trademark) M-930; manufactured by Toyo Seiya Kabushiki Kaisha)

Polymerizable compound (C-4): dipentaerythritol hexaacrylate (average number of equivalents of ethylenically unsaturated groups 96.4; KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemicals, Ltd.)

Polymerization initiator (D-1): n-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-one-2-imine (PBG-327; oxime compound; manufactured by Changzhou powerful new electronic Material Co., Ltd.)

Polymerization initiator (D-2): 1- [ 7- (2-methylbenzoyl) -9, 9-dipropyl-9H-fluoren-2-yl ] ethanone O-acetyloxime (DFI-091; oxime compound; manufactured by DAITO CHEMIX Co., Ltd.)

Polymerization initiator (D-3): n-acetoxy-1- [ 9-ethyl-6- { 2-methyl-4- (3, 3-dimethyl-2, 4-dioxopentylmethoxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine (N-1919; oxime Compound; manufactured by ADEKA Co., Ltd.)

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 SH 8400; manufactured by Dow Corning Toray Co., Ltd.)

[ preparation of colored coating film ]

The colored curable resin composition was applied onto a 5cm square glass substrate (EAGLE 2000; manufactured by CORNING) by spin coating so that the film thickness after postbaking was 2.0. mu.m, and then prebaked at 100 ℃ for 3 minutes to form a colored composition layer. After cooling, the resultant was exposed to 100mJ/cm in an air atmosphere using an exposure machine (TME-150 RSK; manufactured by TOPCON Ltd.) ² The exposure amount (365nm basis) of (b) is irradiated with light to the colored composition layer. Thereafter, the resultant was postbaked in an oven at 230 ℃ for 30 minutes to obtain a colored coating film.

[ evaluation of contrast ]

The obtained colored coating film was measured for contrast with a contrast meter (CT-1; manufactured by Zusamaso K.K., color difference meter BM-5A; manufactured by TOPCON K.K., illuminant; F-10, polarizing film; manufactured by Zusamaso K.K.) with a blank value of 30000. The results are shown in tables 16 to 17.

[ Table 16]

[ Table 17]

In summary, when a prescribed amount of the squarylium dye and a prescribed amount of the polymerizable compound are used as the colorant, the contrast is improved. On the other hand, when the amount of the polymerizable compound is increased, the amount of the polymerization initiator is decreased, and the contrast is further improved.

Claims

1. A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D),

the colorant (A) comprises a squaric acid

A dye, a water-soluble dye and a water-soluble dye,

the squaric acid

The amount of the dye is 3 to 140 parts by mass per 100 parts by mass of the polymerization initiator (D),

< average number of equivalents of ethylenically unsaturated group >

In the formula (1), the acid-base catalyst,

K _i a value represented by (molecular weight/number of ethylenically unsaturated bonds) of the i component in all the polymerizable compounds (C) contained in the colored curable resin composition,

m _i represents the mole fraction of the component i.

2. The colored curable resin composition according to claim 1, wherein the squaric acid

The dye comprises at least 1 selected from the group consisting of a compound represented by the formula (I) and a compound represented by the formula (III),

in the formula (I), the compound is shown in the specification,

R ¹ ～R ⁸ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms which may have a substituent,

R ⁹ and R ¹⁰ Each independently represents an optionally substituted 2-valent aliphatic hydrocarbon group having 1 to 20 carbon atomsThe methylene group contained may be substituted by-O-,

R ¹¹ and R ¹² Each independently represents a hydrocarbon group having 6 to 20 carbon atoms and an aromatic hydrocarbon ring, the hydrocarbon group may have a substituent, a methylene group contained in the hydrocarbon group may be substituted by-O-,

R ¹³ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms,

in the formula (III), the compound represented by the formula (III),

R ³¹ ～R ³⁸ each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms which may have a substituent,

R ³⁹ ～R ⁴² each independently represents a C1-20 hydrocarbon group which may have a substituent, R ³⁹ ～R ⁴² At least one of the above groups is an aliphatic hydrocarbon group having 1 to 20 carbon atoms and having a carboxyl group as a substituent, and R ³⁹ ～R ⁴² At least one of the aliphatic hydrocarbon groups is an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, and the methylene group contained in the aliphatic hydrocarbon group may be substituted by-O-.

3. The colored curable resin composition according to claim 1 or 2, wherein the average number of equivalents of ethylenically unsaturated groups is 83.0 or more.

4. 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 to 5 ethylenically unsaturated bonds.

5. The colored curable resin composition according to any one of claims 1 to 4, wherein the polymerizable compound (C) comprises at least 1 selected from pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and glycerol tri (meth) acrylate.

6. The colored curable resin composition according to any one of claims 1 to 5, wherein the polymerization initiator (D) comprises an O-acyloxime compound.

7. A color filter comprising the colored curable resin composition according to any one of claims 1 to 6.

8. A display device comprising the color filter of claim 7.

9. A solid-state imaging element comprising the color filter according to claim 7.