WO2020105346A1

WO2020105346A1 - Colored composition, colored curable resin composition, color filter, and display device

Info

Publication number: WO2020105346A1
Application number: PCT/JP2019/041451
Authority: WO
Inventors: 裕史濱木; 学栂井
Original assignee: 住友化学株式会社
Priority date: 2018-11-21
Filing date: 2019-10-23
Publication date: 2020-05-28
Also published as: JP2020083981A; TWI799661B; TW202030264A; KR20210093248A; CN113056525B; CN113056525A; JP7241514B2

Abstract

The present invention addresses the problem of providing a colored composition having satisfactory heat resistance and light resistance.　The present invention relates to a colored composition comprising a resin and a compound represented by formula (I).

Description

Coloring composition, coloring curable resin composition, color filter and display device

The present invention relates to a colored composition, a colored curable resin composition, a color filter and a display device.

It has been proposed in the field of gas separation membranes that potassium salt of perylenetetracarboxylic acid is excellent in CO ₂ separation ability (Non-Patent Document 1).

Improvement of heat resistance and light resistance is required in the field of colorants.

The object of the present invention is to provide a colored composition having good heat resistance and light resistance.

The present invention provides the following [1] to [4].
[1] A coloring composition containing a compound represented by the following formula (I) and a resin.

[In the formula,
R ¹ to R ³ each independently represent a hydrogen atom, —CO ₂ ^— , a halogen atom, a cyano group, a nitro group, or a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.
R ⁴ to R ¹¹ are each independently a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a hydrogen atom, a halogen atom, cyano. group, a nitro group, -CO ₂ ^-, or -S (O) ₂ O ^- represents a.
-CH _2- which is contained in the hydrocarbon group having 1 to 40 carbon atoms and may have a substituent represented by R ⁴ to R ¹¹ and does not form a ring, and R ⁴ to R ¹¹ The —CH ₂ — contained in the heterocyclic group which may have a substituent and does not form a ring is —O—, —CO—, —S (O) ₂ —, —NR ^x1 — May be replaced with. However, -COOH and -S (O) ₂ OH are not formed by replacing -CH _2- .
R ^x1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
M ^{x +} represents a hydron or an x-valent metal cation.
x represents an integer of 2 or more.
a represents the valence of the structure in parentheses with a, and represents an integer of 1 or more and 12 or less.
b represents the number of M ^{X +} and represents an integer of 1 or more and 12 or less.
a and b are the following formulas:
a = bx
Meet ]
[2] A colored curable resin composition containing the colored composition according to [1], a polymerizable compound, a polymerization initiator, and a solvent.
[3] A color filter formed from the colored curable resin composition according to [2].
[4] A display device including the color filter according to [3].

According to the present invention, a colored composition having good heat resistance and light resistance is provided.

<Coloring composition>
The colored composition of the present invention contains a compound represented by the formula (I) (hereinafter, also referred to as compound (I)) and a resin (hereinafter, also referred to as resin (B)).

Compound (I) also includes its tautomers and salts thereof.
The compound (I) can be used as a colorant.
The colored composition of the present invention may contain one or more compounds (I).
The coloring composition of the present invention may contain a solvent (hereinafter sometimes referred to as solvent (E)).
Further, the compound (I) is preferably dispersed in the solvent (E).
The coloring composition of the present invention may contain a colorant other than compound (I) (hereinafter, also referred to as colorant (A1)) (hereinafter, compound (I) is combined with colorant (A1). Also referred to as a coloring agent (A)).
The colorant (A1) may contain one or more kinds of colorants.
The colorant (A1) preferably contains a yellow colorant and / or an orange colorant and / or a red colorant.
In addition, the colored curable resin composition of the present invention includes a compound (I), a resin (B), a polymerizable compound (hereinafter, also referred to as a polymerizable compound (C)), a polymerization initiator (hereinafter, a polymerization initiator (D). )) And a solvent (E). In other words, the colored curable resin composition of the present invention contains the colored composition of the present invention, the polymerizable compound (C), the polymerization initiator (D) and the solvent (E).
The colored curable resin composition of the present invention may contain a polymerization initiation auxiliary agent (hereinafter, also referred to as a polymerization initiation auxiliary agent (D1)).
The colored curable resin composition of the present invention may further contain a leveling agent (hereinafter, also referred to as a leveling agent (F)) and an antioxidant.

[Compound (I)]
The compound (I) is a compound represented by the following formula (I).

[In the formula,
R ¹ to R ³ each independently represent a hydrogen atom, —CO ₂ ^— , a halogen atom, a cyano group, a nitro group, or a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.
R ⁴ to R ¹¹ are each independently a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a hydrogen atom, a halogen atom, cyano. group, a nitro group, -CO ₂ ^-, or -S (O) ₂ O ^- represents a.
-CH _2- which is contained in the hydrocarbon group having 1 to 40 carbon atoms and may have a substituent represented by R ⁴ to R ¹¹ and does not form a ring, and R ⁴ to R ¹¹ The —CH ₂ — contained in the heterocyclic group which may have a substituent and does not form a ring is —O—, —CO—, —S (O) ₂ —, —NR ^x1 — May be replaced with. However, -COOH and -S (O) ₂ OH are not formed by replacing -CH _2- .
R ^x1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
The hydrocarbon group represented by R ⁴ to R ¹¹ and having 1 to 40 carbon atoms which may have a substituent and the heterocyclic group which may have a substituent include —CO ₂ ^— and —S It may have at least one selected from the group consisting of (O) ₂ O ⁻ .
M ^{x +} represents a hydron or an x-valent metal cation.
x represents an integer of 2 or more.
a represents the valence of the structure in parentheses with a, and represents an integer of 1 or more and 12 or less.
b represents the number of M ^{X +} and represents an integer of 1 or more and 12 or less.
a and b are the following formulas:
a = bx
Meet ]

Examples of the halogen atom represented by R ¹ to R ³ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Of these, a fluorine atom and a chlorine atom are preferable.

The hydrocarbon group represented by R ¹ to R ³ has 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 15 carbon atoms, It is preferably 1 to 10.

The hydrocarbon group having 1 to 40 carbon atoms represented by R ¹ to R ³ represents an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be saturated or unsaturated. Well, it may be a chain or a ring (alicyclic hydrocarbon group).

Examples of the saturated or unsaturated chain aliphatic hydrocarbon group represented by R ¹ to R ³ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group , Heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, hentriacontyl group, dotriacontyl group, tritriacontyl group, tetratriacontyl group, pentatriacontyl group, hexatriacontyl group, heptatriacontyl group, Linear alkyl groups such as octatriacontyl group, nonatriacontyl group and tetracontyl group; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, (2-ethyl) butyl group, isopentyl group, neopentyl group Group, tert-pentyl group, (1-methyl) pentyl group, (2-methyl) pentyl group, (1-ethyl) pentyl group, (3-ethyl) pentyl group, isohexyl group, (5-methyl) hexyl group, Branched chain alkyl groups such as (2-ethyl) hexyl group and (3-ethyl) heptyl group; vinyl group, 1-propenyl group, 2-propenyl group (allyl group), (1-methyl) ethenyl group An alkenyl group such as 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, (1- (2-propenyl)) ethenyl group, (1,2-dimethyl) propenyl group, 2-pentenyl group; Etc. The saturated or unsaturated chain hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, further preferably 1 to 15 carbon atoms, and particularly preferably 1 to 10 carbon atoms.
Of these, a linear or branched alkyl group having 1 to 8 carbon atoms is more preferable, and a methyl group or an ethyl group is particularly preferable.

Examples of the saturated or unsaturated alicyclic hydrocarbon group represented by R ¹ to R ³ include cyclopropyl group, 1-methylcyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 1-methylcyclohexyl group. Group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 1,2-dimethylcyclohexyl group, 1,3-dimethylcyclohexyl group, 1,4-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group Group, 2,4-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,2-dimethylcyclohexyl group, 3,3-dimethylcyclohexyl group, 4,4-dimethylcyclohexyl group, cyclooctyl group, 2,4,6-trimethylcyclohexyl group, 2,2,6,6-tetramethylcyclohexyl group, 3,3,5,5 A cycloalkyl group such as tetramethylcyclohexyl group, 4-pentylcyclohexyl group, 4-octylcyclohexyl group, 4-cyclohexylcyclohexyl group; cyclohexenyl group (eg cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl group, Examples include cycloalkenyl groups such as cyclooctenyl groups; norbornane groups, adamantyl groups, bicyclo [2.2.2] octane, and the like. The saturated or unsaturated alicyclic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, further preferably 4 to 20 carbon atoms, and particularly preferably 4 to 15 carbon atoms. It is more preferably 5 to 15, and particularly preferably 5 to 10. Of these, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are most preferable.

Examples of the aromatic hydrocarbon group represented by R ¹ to R ³ include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethyl group. Phenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group , 4-vinylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, o-tert-butylphenyl group, m-tert-butylphenyl group, p-tert-butylphenyl group, 3 , 5-di (tert-butyl) phenyl group, mesityl group, 4-ethylphenyl group, 4-butylphenyl group, 4-pentylphenyl group, 2,6-bis (2-propyl) phenyl group, 4-cyclohexylphenyl Group, 2,4,6-trimethylphenyl group, 4-octylphenyl group, 4- (2,4,4-trimethyl-2-pentyl) phenyl group, 1-naphthyl group, 2-naphthyl group, 5,6 7,8-Tetrahydro-1-naphthyl group, 5,6,7,8-tetrahydro-2-naphthyl group, fluorenyl group, phenanthryl group, anthryl group, 2-dodecylphenyl group, 3-dodecylphenyl group, 4-dodecyl Aromatic hydrocarbon groups such as phenyl group and pyrenyl group; and the like. The aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and further preferably 6 to 15 carbon atoms.

The hydrocarbon group represented by R ¹ to R ³ is a group in which two or more of the above-mentioned hydrocarbon groups are combined, for example, at least an aromatic hydrocarbon group, a chain hydrocarbon group and an alicyclic hydrocarbon group. And aralkyl groups such as benzyl group, phenethyl group and 1-methyl-1-phenylethyl group; arylalkenyl groups such as phenylethenyl group (phenylvinyl group); An arylalkynyl group such as a phenylethynyl group; a phenyl group to which one or more phenyl groups such as a biphenylyl group and a terphenylyl group are bonded; a cyclohexylmethylphenyl group, a benzylphenyl group, and a (dimethyl (phenyl) methyl) phenyl group. .

The hydrocarbon group represented by R ¹ to R ³ may be a group in which two or more of the above-mentioned hydrocarbon groups are combined, for example, a group in which a chain hydrocarbon group and an alicyclic hydrocarbon group are combined. As examples thereof, cyclopropylmethyl group, cyclopropylethyl group, cyclobutylmethyl group, cyclobutylethyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclohexylmethyl group, 2-methylcyclohexylmethyl group, cyclohexylethyl group, adamantylmethyl group And an alkyl group to which one or more alicyclic hydrocarbon groups such as groups are bonded.

The group consisting of two or more of the above hydrocarbon groups has preferably 4 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, further preferably 4 to 15 carbon atoms, and further preferably 6 to 15 carbon atoms.

Examples of the substituent which the hydrocarbon group having 1 to 40 carbon atoms represented by R ¹ to R ³ may have include, for example, halogen atom, formyl group, carboxy group, formyloxy group, hydroxy group, thiol. Group, sulfo group, sulfamoyl group, pentafluorosulfanyl group, carbamoyl group, amino group, nitro group, cyano group, —COR ¹² , —COOR ¹² , —OCOR ¹² , —OR ¹² , —SR ¹² , —SOR ¹² , — SO ₂ R ¹² , -SO ₂ NHR ¹² , -SO ₂ NR ¹² R ¹³ , -CONHR ¹² , -CONR ¹² R ¹³ , -NHR ¹² ,-
NR ¹² R ¹³ , —NHCOR ¹² , —NR ¹³ COR ^{12 and the} like can be mentioned.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Of these, a fluorine atom and a chlorine atom are preferable.

R ¹² and R ¹³ each independently represent an alkyl group, a phenyl group or a naphthyl group.

The alkyl group represented by R ¹² and R ¹³ preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and further preferably 1 to 5 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and tridecyl group. , Tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like.

—COR ¹² includes, for example, acetyl group, propanoyl group, butanoyl group, 2,2-dimethylpropanoyl group, pentanoyl group, hexanoyl group, (2-ethyl) hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group. , Undecanoyl group, dodecanoyl group, henicosanoyl group, benzoyl group and the like.

—COOR ¹² includes, for example, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, tert-butoxycarbonyl group, butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, (2-ethyl) hexyloxycarbonyl group, heptyl. Examples thereof include an oxycarbonyl group, an octyloxycarbonyl group, a nonyloxycarbonyl group, a decyloxycarbonyl group, an undecyloxycarbonyl group, a dodecyloxycarbonyl group, a phenyloxycarbonyl group and an icosyloxycarbonyl group.

—OCOR ¹² includes, for example, an acetoxy group, a propanoyloxy group, a butanoyloxy group, a 2,2-dimethylpropanoyloxy group, a pentanoyloxy group, a hexanoyloxy group, a (2-ethyl) hexanoyloxy group, Heptanoyloxy group, octanoyloxy group, nonanoyloxy group, decanoyloxy group, undecanoyloxy group, dodecanoyloxy group, henicosanoyloxy group, benzoyloxy group, ethenylcarbonyloxy group, 2-propenylcarbonyl group An oxy group etc. are mentioned.

Examples of —OR ¹² include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a phenoxy group and a naphthyloxy group.

—SR ¹² includes, for example, methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, butylsulfanyl group, tert-butylsulfanyl group, pentylsulfanyl group, hexylsulfanyl group, (2-ethyl) hexylsulfanyl group, heptylsulfanyl group, Examples thereof include an octylsulfanyl group, a nonylsulfanyl group, a decylsulfanyl group, an undecylsulfanyl group, a dodecylsulfanyl group, an icosylsulfanyl group, a phenylsulfanyl group and an o-tolylsulfanyl group.

Examples of —SOR ¹² include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, a butylsulfinyl group, a pentylsulfinyl group, a phenylsulfinyl group, and a naphthylsulfinyl group.

Examples of —SO ₂ R ¹² include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, a pentylsulfonyl group, a phenylsulfonyl group, and a naphthylsulfonyl group.

—SO ₂ NHR ¹² includes, for example, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N -Isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N-hexylsulfyl group Famoyl group, N- (2-ethyl) hexylsulfamoyl group, N-heptylsulfamoyl group, N-octylsulfamoyl group, N-nonylsulfamoyl group, N-decylsulfamoyl group, N -Undecylsulfamoyl group, N-dodecylsulfamoyl group, N-icosylsulfamoyl group, N-phenylsulfamoyl group and the like can be mentioned.

--SO ₂ NR ¹² R ¹³ is, for example, N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group. Moyl group, N, N-dipropylsulfamoyl group, N, N-isopropylmethylsulfamoyl group, N, N-diisopropylsulfamoyl group, N, N-tert-butylmethylsulfamoyl group, N, N -Diisobutylsulfamoyl group, N, N-disec-butylsulfamoyl group, N, N-ditert-butylsulfamoyl group, N, N-butylmethylsulfamoyl group, N, N-dibutylsulfyl group Famoyl group, N, N-dipentylsulfamoyl group, N, N-di (1-ethylpropyl) sulfamoyl group, N, N-dihexylsulfamoyl group, N, N-di (2-ethyl) hexylsul Famoyl group, N, N-diheptylsulfamoyl group, N, N-octylmethylsulfamoyl group, N, N-dioctylsulfamoyl group, N, N-dinonylsulfamoyl group, N, N- Decylmethylsulfamoyl group, N, N-undecylmethylsulfamoyl group, N, N-dodecylmethylsulfamoyl group, N, N-icosylmethylsulfamoyl group, N, N-phenylmethylsulfa group Examples thereof include moyl group and N, N-diphenylsulfamoyl group.

-CONHR ¹² is, for example, N-methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N-isopropylcarbamoyl group, N-butylcarbamoyl group, N-isobutylcarbamoyl group, N-sec-butylcarbamoyl group. , N-tert-butylcarbamoyl group, N-pentylcarbamoyl group, N- (1-ethylpropyl) carbamoyl group, N-hexylcarbamoyl group, N- (2-ethyl) hexylcarbamoyl group, N-heptylcarbamoyl group, N -Octylcarbamoyl group, N-nonylcarbamoyl group, N-decylcarbamoyl group, N-undecylcarbamoyl group, N-dodecylcarbamoyl group, N-icosylcarbamoyl group, N-phenylcarbamoyl group and the like can be mentioned.

-CONR ¹² R ¹³ is an N, N-dimethylcarbamoyl group, N, N-ethylmethylcarbamoyl group, N, N-diethylcarbamoyl group, N, N-propylmethylcarbamoyl group, N, N-dipropylcarbamoyl group. , N, N-isopropylmethylcarbamoyl group, N, N-diisopropylcarbamoyl group, N, N-tert-butylmethylcarbamoyl group, N, N-diisobutylcarbamoyl group, N, N-disec-butylcarbamoyl group, N, N-ditert-butylcarbamoyl group, N, N-butylmethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-butyloctylcarbamoyl group, N, N-dipentylcarbamoyl group, N, N-di (1 -Ethylpropyl) carbamoyl group, N, N-dihexylcarbamoyl group, N, N-di (2-ethyl) hexylcarbamoyl group, N, N-diheptylcarbamoyl group, N, N-octylmethylcarbamoyl group, N, N -Dioctylcarbamoyl group, N, N-dinonylcarbamoyl group, N, N-decylmethylcarbamoyl group, N, N-undecylmethylcarbamoyl group, N, N-dodecylmethylcarbamoyl group, N, N-icosylmethylcarbamoyl group Group, N, N-phenylmethylcarbamoyl group, N, N-diphenylcarbamoyl group and the like.

-NHR ¹² is, for example, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-isobutylamino group, N-sec-butylamino group. , N-tert-butylamino group, N-pentylamino group, N-hexylamino group, N- (2-ethyl) hexylamino group, N-heptylamino group, N-octylamino group, N-nonylamino group, N -Decylamino group, N-undecylamino group, N-dodecylamino group, N-icosylamino group, N-phenylamino group and the like.

—NR ¹² R ¹³ is, for example, N, N-dimethylamino group, N, N-ethylmethylamino group, N, N-diethylamino group, N, N-propylmethylamino group, N, N-dipropylamino group. , N, N-isopropylmethylamino group, N, N-diisopropylamino group, N, N-tert-butylmethylamino group, N, N-diisobutylamino group, N, N-disec-butylamino group, N, N-ditert-butylamino group, N, N-butylmethylamino group, N, N-dibutylamino group, N, N-dipentylamino group, N, N-di (1-ethylpropyl) amino group, N, N-dihexylamino group, N, N-di (2-ethyl) hexylamino group, N, N-diheptylamino group, N, N-dioctylamino group, N, N-dinonylamino group, N, N-decylmethyl group Amino group, N, N-undecylmethylamino group, N, N-dodecylmethylamino group, N, N-icosylmethylamino group, N, N-phenylmethylamino group, N, N-diphenylamino group, etc. Can be mentioned.

—NHCOR ¹² includes, for example, acetylamino group, propanoylamino group, butanoylamino group, 2,2-dimethylpropanoylamino group, pentanoylamino group, hexanoylamino group, (2-ethyl) hexanoylamino group. , Heptanoylamino group, octanoylamino group, nonanoylamino group, decanoylamino group, undecanoylamino group, dodecanoylamino group, henicosanoylamino group, benzoylamino group and the like.
Examples of —NR ¹³ COR ¹² include an N-methyl-N-acetylamino group.
R ¹ ~ R ³ are preferably, independently of one another, -CO ₂ ^-, a halogen atom, a cyano group, a hydrocarbon group of a nitro group or a carbon atoms which may have a substituent ~ 40, R ¹ At least one of to R ³ represents —CO ₂ ^— .
R ¹ to R ³ more preferably independently of each other represent —CO ₂ ^— , a halogen atom, a cyano group or a nitro group, and at least one of R ¹ to R ³ represents —CO ₂ ^— .
R ¹ to R ³ are more preferably, independently of each other, R ¹ and R ³ are the same and represent —CO ₂ ^— , a halogen atom, a cyano group or a nitro group, and R ² are —CO ₂ ^— .

Examples of the halogen atom represented by R ⁴ to R ¹¹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Of these, a fluorine atom and a chlorine atom are preferable.

The hydrocarbon group having 1 to 40 carbon atoms represented by R ⁴ to R ¹¹ represents an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be saturated or unsaturated. Well, it may be chain-like or cyclic.

Examples of the saturated or unsaturated chain aliphatic hydrocarbon group represented by R ⁴ to R ¹¹ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group , Heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, hentriacontyl group, dotriacontyl group, tritriacontyl group, tetratriacontyl group, pentatriacontyl group, hexatriacontyl group, heptatriacontyl group, Linear alkyl groups such as octatriacontyl group, nonatriacontyl group and tetracontyl group; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, (2-ethyl) butyl group, isopentyl group, neopentyl group Group, tert-pentyl group, (1-methyl) pentyl group, (2-methyl) pentyl group, (1-ethyl) pentyl group, (3-ethyl) pentyl group, isohexyl group, (5-methyl) hexyl group, Branched chain alkyl groups such as (2-ethyl) hexyl group and (3-ethyl) heptyl group; vinyl group, 1-propenyl group, 2-propenyl group (allyl group), (1-methyl) ethenyl group An alkenyl group such as 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, (1- (2-propenyl)) ethenyl group, (1,2-dimethyl) propenyl group, 2-pentenyl group; Etc.
The saturated or unsaturated chain hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, further preferably 1 to 15 carbon atoms, and particularly preferably 1 to 10 carbon atoms. Of these, a linear or branched alkyl group having 1 to 8 carbon atoms is more preferable, and a methyl group or an ethyl group is particularly preferable.

Examples of the saturated or unsaturated alicyclic hydrocarbon group represented by R ⁴ to R ¹¹ include cyclopropyl group, 1-methylcyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 1-methylcyclohexyl group. Group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 1,2-dimethylcyclohexyl group, 1,3-dimethylcyclohexyl group, 1,4-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group Group, 2,4-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,2-dimethylcyclohexyl group, 3,3-dimethylcyclohexyl group, 4,4-dimethylcyclohexyl group, cyclooctyl group, 2,4,6-trimethylcyclohexyl group, 2,2,6,6-tetramethylcyclohexyl group, 3,3,5,5 A cycloalkyl group such as tetramethylcyclohexyl group, 4-pentylcyclohexyl group, 4-octylcyclohexyl group, 4-cyclohexylcyclohexyl group; cyclohexenyl group (eg cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl group, Examples include cycloalkenyl groups such as cyclooctenyl groups; norbornane groups, adamantyl groups, bicyclo [2.2.2] octane, and the like. The saturated or unsaturated alicyclic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, further preferably 4 to 20 carbon atoms, and particularly preferably 4 to 15 carbon atoms. It is more preferably 5 to 15, and particularly preferably 5 to 10. Of these, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are most preferable.

Examples of the aromatic hydrocarbon group represented by R ⁴ to R ¹¹ include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethyl group. Phenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group , 4-vinylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, o-tert-butylphenyl group, m-tert-butylphenyl group, p-tert-butylphenyl group, 3 , 5-di (tert-butyl) phenyl group, mesityl group, 4-ethylphenyl group, 4-butylphenyl group, 4-pentylphenyl group, 2,6-bis (2-propyl) phenyl group, 4-cyclohexylphenyl Group, 2,4,6-trimethylphenyl group, 4-octylphenyl group, 4- (2,4,4-trimethyl-2-pentyl) phenyl group, 1-naphthyl group, 2-naphthyl group, 5,6 7,8-Tetrahydro-1-naphthyl group, 5,6,7,8-tetrahydro-2-naphthyl group, fluorenyl group, phenanthryl group, anthryl group, 2-dodecylphenyl group, 3-dodecylphenyl group, 4-dodecyl Aromatic hydrocarbon groups such as phenyl group and pyrenyl group; and the like. The aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and further preferably 6 to 15 carbon atoms.

The hydrocarbon group represented by R ⁴ to R ¹¹ is a group in which two or more of the above hydrocarbon groups are combined, for example, at least an aromatic hydrocarbon group, a chain hydrocarbon group and an alicyclic hydrocarbon group. And aralkyl groups such as benzyl group, phenethyl group and 1-methyl-1-phenylethyl group; arylalkenyl groups such as phenylethenyl group (phenylvinyl group); An arylalkynyl group such as a phenylethynyl group; a phenyl group to which one or more phenyl groups such as a biphenylyl group and a terphenylyl group are bonded; a cyclohexylmethylphenyl group, a benzylphenyl group, a (dimethyl (phenyl) methyl) phenyl group and the like. ..

The hydrocarbon group represented by R ⁴ to R ¹¹ may be a group in which two or more of the above-mentioned hydrocarbon groups are combined, for example, a group in which a chain hydrocarbon group and an alicyclic hydrocarbon group are combined. As examples thereof, cyclopropylmethyl group, cyclopropylethyl group, cyclobutylmethyl group, cyclobutylethyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclohexylmethyl group, 2-methylcyclohexylmethyl group, cyclohexylethyl group, adamantylmethyl group And an alkyl group to which one or more alicyclic hydrocarbon groups such as groups are bonded.

The heterocyclic group represented by R ⁴ to R ¹¹ may be monocyclic or polycyclic. Examples of the hetero atom in the heterocyclic group include a nitrogen atom, an oxygen atom and a sulfur atom.

The heterocyclic group represented by R ⁴ to R ¹¹ preferably has 1 to 20 carbon atoms, more preferably 3 to 18 carbon atoms, further preferably 3 to 16 carbon atoms, and particularly preferably 3 to 14 carbon atoms. Yes, and more preferably 3 to 12.

Examples of the heterocycle in the heterocyclic group containing a nitrogen atom include monocyclic saturated heterocycles such as aziridine, azetidine, pyrrolidine, piperidine and piperazine; pyrrole, pyrazole, imidazole, 1,2,3-triazole and 1,2,4. 5-membered unsaturated heterocycles such as triazole; 6-membered unsaturated heterocycles such as pyridine, pyridazine, pyrimidine, pyrazine and 1,3,5-triazine; indazole, indoline, isoindoline, indole, indolizine , Benzimidazole, quinoline, isoquinoline, 5,6,7,8-tetrahydroquinoxaline, quinoxaline, quinazoline, cinnoline, phthalazine, naphthyridine, purine, pteridine, benzopyrazole, benzopiperidine, etc. fused bicyclic heterocycles; carbazole, acridine And fused tricyclic heterocycles such as phenazine; and the like.

Examples of the heterocycle in the heterocyclic group containing an oxygen atom include monocyclic saturated heterocycles such as oxirane, oxetane, tetrahydrofuran, tetrahydropyran, 1,3-dioxane and 1,4-dioxane, 1,3-dioxolane; Bicyclic saturated heterocycles such as 4-dioxaspiro [4.5] decane and 1,4-dioxaspiro [4.4] nonane; α-acetolactone, β-propiolactone, γ-butyrolactone, γ-valerolactone and Lactone-based heterocycles such as δ-valerolactone; 5-membered unsaturated heterocycles such as furan; 6-membered unsaturated heterocycles such as 2H-pyran and 4H-pyran; 1-benzofuran, benzopyran, benzodioki And condensed bicyclic heterocycles such as sole, chroman and isochroman; condensed tricyclic heterocycles such as xanthene and dibenzofuran; and the like.

The heterocycle in the heterocyclic group containing a sulfur atom includes a 5-membered saturated heterocycle such as dithiolane; a 6-membered saturated heterocycle such as thiane and 1,3-dithiane; thiophene, 4H-thiopyran, benzotetrahydrothio. 5-membered ring unsaturated heterocycles such as pyran; condensed bicyclic heterocycles such as benzothiophene; condensed tricyclic heterocycles such as thianthrene and dibenzothiophene; and the like.

Examples of the heterocycle in the heterocyclic group containing a nitrogen atom and an oxygen atom include monocyclic saturated heterocycles such as morpholine, 2-pyrrolidone and 2-piperidone; monocyclic unsaturated heterocycles such as oxazole and isoxazole; benzoxazole , A condensed bicyclic heterocycle such as benzisoxazole, benzoxazine, benzodioxane, and benzimidazoline; a condensed tricyclic heterocycle such as phenoxazine; and the like.

Examples of the heterocycle in the heterocyclic group containing a nitrogen atom and a sulfur atom include a monocyclic heterocycle such as thiazole; a condensed bicyclic heterocycle such as benzothiazole; a condensed tricyclic heterocycle such as phenothiazine; and the like. ..

Note that the bonding position of the above heterocyclic group is a portion where any hydrogen atom contained in each heterocycle is eliminated.

The above heterocyclic group may be a group in which two or more of the above-exemplified heterocyclic group and the above-exemplified hydrocarbon group are combined, and examples thereof include a tetrahydrofurylmethyl group.

Examples of the substituent which the hydrocarbon group having 1 to 40 carbon atoms represented by R ⁴ to R ¹¹ and the heterocyclic group may have include, for example, a halogen atom, a formyl group, a formyloxy group, a hydroxy group, Carboxy group, thiol group, sulfo group, sulfamoyl group, pentafluorosulfanyl group, carbamoyl group, amino group, nitro group, cyano group, -COR ¹² , -COOR ¹² , -OCOR ¹² , -OR ¹² , -SR ¹² ,- SOR ¹² , -SO ₂ R ¹² , -SO ₂ NHR ¹² , -SO ₂ NR ¹² R ¹³ , -CONHR ¹² , -CONR ¹² R ¹³ , -NHR ¹² , -NR ¹² R ¹³ , -NHCOR ¹² , -NR ¹³ COR ^{12 and the} like can be mentioned. Examples of R ¹² and R ¹³ include the same examples as the alkyl group, phenyl group or naphthyl group exemplified above.

Examples of the substituent which the hydrocarbon group represented by R ⁴ to R ¹¹ and having 1 to 40 carbon atoms and the heterocyclic group may have are those having 1 carbon atom represented by R ¹ to R ³ above. It is the same as the example in the description of the substituents which the hydrocarbon groups of 40 may have.

Included in a hydrocarbon group having 1 to 40 carbon atoms represented by R ⁴ to R ¹¹ and not forming a ring, —CH ₂ —, and contained in a heterocyclic group represented by R ⁴ to R ¹¹ , and —CH ₂ which does not form a ring may be replaced with —O—, —CO—, —S (O) ₂ —, or —NR ^x1 —. However, replacement of —CH ₂ — does not form —COOH and —S (O) ₂ OH. R ^x1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, isopropyl group, isobutyl group, sec-butyl group and isopentyl group.

Examples of R ⁴ to R ¹¹ include groups represented by the following formulas. * Represents a bond.

R ⁴ to R ¹¹ are preferably hydrogen atom, halogen atom, hydroxy group, nitro group, cyano group, —CH ₃ , formulas (Aa-1) to (Aa-18), (Ba-1) to (Ba). -27), (Ca-1) to (Ca-18) and (Da-1) to (Da-27).

M ^{x +} represents a hydron or an x-valent metal cation. x represents an integer of 2 or more, preferably 2 or more and 4 or less.

Examples of the divalent metal cation (M ²⁺ ) include Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Cd ²⁺ , Fe ²⁺ , Co ²⁺ , Rh ²⁺ , Ir ²⁺ , Examples thereof include Ni ²⁺ , Pd ²⁺ , Cu ²⁺ , Zn ²⁺ , Hg ²⁺ , Sn ²⁺ , Pb ²⁺ and Mn ²⁺ .

Examples of the trivalent metal cation (M ³⁺ ) include Cr ³⁺ , Fe ³⁺ , Co ³⁺ and Al ³⁺ .

Examples of the tetravalent metal cation (M ⁴⁺ ) include Ti ⁴⁺ , Zr ⁴⁺ , Hf ⁴⁺ , Mn ⁴⁺ , Si ⁴⁺ , Ge ⁴⁺ , Sn ⁴⁺ and Pb ⁴⁺ .

Specific examples of the compound (I) include the compounds shown in Tables 1 to 3 below.

Of these, compounds represented by the following formulas (I-1) to (I-5) are preferable.

From the viewpoints of heat resistance and light resistance, compounds represented by formula (I-1), formula (I-2), formula (I-3) and formula (I-5) are more preferable.

The compound (I) can be produced, for example, by reacting a compound represented by the following formula (pt1) with water. Alternatively, compound (I) is produced, for example, by reacting a product obtained by reacting a compound represented by the following formula (pt1) with water, and a compound represented by the following formula (M1). be able to.

[In the formula, R ⁴ to R ¹¹ are the same as defined above. ]

Examples of the compound represented by the formula (pt1) include 3,4,9,10-perylenetetracarboxylic dianhydride. The amount of water used is usually 2 mol or more and 20 mol or less, preferably 2 mol or more and 16 mol or less, and more preferably 2 mol or more and 10 mol with respect to 1 mol of the compound represented by the formula (pt1). It is below, and more preferably from 2 mol to 8 mol.

The reaction between the compound represented by the following formula (pt1) and water is usually carried out in the presence of a base and a solvent. Examples of the base include triethylamine, 4- (N, N-dimethylamino) pyridine, pyridine, piperidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3]. .0] non-5-ene, 1,5-diazabicyclo [4.3.0] non-5-ene and other organic bases, methyllithium, butyllithium, tert-butyllithium, phenyllithium and other organometallic compounds; Inorganic bases such as sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, and potassium hydroxide can be mentioned.

The amount of the base used is usually 1 mol or more and 20 mol or less, preferably 1 mol or more and 16 mol or less, and more preferably 1 mol or more and 10 mol, relative to 1 mol of the compound represented by the formula (pt1). It is below, and more preferably 1 to 8 mol.

When the reaction of the compound represented by the following formula (pt1) with water is carried out in the presence of a base, the compound (I) of the present invention can be produced by neutralizing with an acid at the end of the reaction. .. Examples of the acid include inorganic acids such as hydrogen chloride, hydrogen bromide, hydrogen iodide, sulfuric acid, nitric acid, fluorosulfonic acid and phosphoric acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid; Examples thereof include carboxylic acids such as acetic acid, citric acid, formic acid, gluconic acid, lactic acid, oxalic acid and tartaric acid, preferably hydrogen chloride, hydrogen bromide, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and Examples thereof include carboxylic acid.

The amount of the acid used is usually 1 mol or more and 20 mol or less, preferably 1 mol or more and 16 mol or less, and more preferably 1 mol or more and 10 mol per 1 mol of the compound represented by the formula (pt1). It is below, and more preferably 1 to 8 mol.

[In the formula,
M represents hydrone or an x-valent metal cation.
x represents an integer of 2 or more.
p represents an integer of 1 or more. ]

Examples of the compound represented by the formula (M1) include magnesium acetate and barium acetate.

The amount of the compound represented by the formula (M1) used is usually 1 mol or more and 10 mol or less, preferably 1 mol or more and 8 mol or less, relative to 1 mol of the compound represented by the formula (pt1). , More preferably 1 mol or more and 6 mol or less, and further preferably 1 mol or more and 4 mol or less.

Examples of the solvent include water; nitrile solvents such as acetonitrile; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, Alcohol solvent such as 1-octanol and phenol; Ether solvent such as diethyl ether and tetrahydrofuran; Ketone solvent such as acetone and methyl isobutyl ketone; Ester solvent such as ethyl acetate; Aliphatic hydrocarbon solvent such as hexane; Aromatic such as toluene Hydrocarbon solvents; halogenated hydrocarbon solvents such as methylene chloride, chloroform and 1,2-dichlorobenzene; amide solvents such as N, N-dimethylformamide and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide.

The amount of the solvent used is usually 1 to 1000 parts by mass with respect to 1 part by mass of the compound represented by the formula (pt1).

The reaction temperature is usually −100 ° C. or higher and 300 ° C. or lower, preferably −90 ° C. or higher and 200 ° C. or lower, and more preferably −10 ° C. or higher and 150 ° C. or lower.

In the compound (I), R ¹ , R ³ and R ⁴ to R ¹¹ are hydrogen atoms and R ² is —CO ₂ ^— is a diisobutyl 3,9-perylenedicarboxylate (Solvent) represented by the following formula. It can be produced by reacting Green 5) with a base in the presence of a solvent, and then reacting the obtained product with an acid or a compound represented by the formula (M1).

In the compound (I), R ¹ and R ³ are cyano groups, R ² is —CO ₂ ^— , and R ⁴ to R ¹¹ are hydrogen atoms, and the compound is 4,10-dicyano represented by the following formula: It can be produced by reacting diisobutyl perylene-3,9-dicarboxylate with a base in the presence of a solvent, and then reacting the obtained product with an acid or a compound represented by the formula (M1). .

The base, the solvent, the acid, the compound represented by the formula (M1), and the amount thereof used may be the same as those exemplified above. The reaction temperature may be in the temperature range exemplified above.

The method of extracting the compound (I) after the completion of the reaction is not particularly limited, and various known methods can be used. For example, the compound (I) can be taken out by distilling off the solvent.
Furthermore, after distilling off the solvent, the obtained residue may be purified by column chromatography, recrystallization or the like. Further, the compound (I) can be taken out by filtration after completion of the reaction.
Further, after filtration, the obtained residue may be purified by column chromatography, recrystallization or the like. The chemical structure of the obtained compound (I) can be analyzed by a known analysis method and its conditions. Such an analysis method is not particularly limited, and examples thereof include an X-ray crystal structure analysis method, a mass spectrometry method (LC), an NMR analysis method and an elemental analysis method. The X-ray crystal structure analysis method is described in, for example, Chemistry of Materials, 2012, Vol. 24, p. It can be performed according to 4647-4652.

The content of the compound (I) in the coloring composition may be, for example, 0.1% by mass or more and 99.9% by mass or less, and preferably 0.5% by mass, based on the total amount of solids in the coloring composition. Mass% or more and 99 mass% or less, more preferably 1 mass% or more and 95 mass% or less, further preferably 5 mass% or more and 90 mass% or less, and particularly preferably 10 mass% or more and 80 mass% or less. Yes, more preferably 15% by mass or more and 70% by mass or less, still more preferably 20% by mass or more and 60% by mass or less, particularly preferably 25% by mass or more and 55% by mass or less, and very preferably 30% by mass. % Or more and 50 mass% or more.
In the present specification, the “total amount of solids in the coloring composition” refers to the total amount of components excluding all solvent components from the coloring composition. The total amount of solid content and the content of each component relative thereto can be measured by a known analysis means such as liquid chromatography or gas chromatography.

[Colorant (A1)]
The coloring composition can contain a colorant (A1) as a colorant other than the compound (I).

The colorant (A1) may contain one kind or two or more kinds of colorants. The colorant (A1) preferably contains a yellow colorant and / or an orange colorant and / or a red colorant.

The colorant (A1) may be a dye or a pigment. As the dye, a known dye can be used, and examples thereof include known dyes described in Color Index (The Society of Dyers and Colorists Publishing) and Dyeing Note (Ishizensha). Further, depending on the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, perylene dyes and the like can be mentioned. You may use these dyes individually or in combination of 2 or more types.

The dyes having the following color index (C.I.) numbers are listed.
Specific examples include dyes having the following color index (CI) numbers.
C. I. Solvent Yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 117, 162, 163, 167, 189;
C. I. Solvent Red 24, 45, 49, 90, 91111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;
C. I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 77, 86, 99;
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, 38, 44, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
C. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and the like C.I. I. Solvent dye,
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;
C. I. Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;
C. I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90: 1, 91, 92, 93, 93: 1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 249, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;
C. I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50: 1, 58, 63, 65, 80, C. 104, 105, 106, 109, etc. I. Acid dyes,
C. I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;
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, 87, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;
C. I. C. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82 and the like. I. Direct dye,
C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse Violet 26, 27;
C. I. C. such as Disperse Blue 1, 14, 56, 60 and the like. I. Disperse dye,
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. C. such as Basic Green 1; I. Basic dye,
C. I. Reactive Yellow 2, 76, 116;
C. I. Reactive Orange 16;
C. I. C. such as Reactive Red 36; I. Reactive dye,
C. I. Modant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Mordan tread 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38 , 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;
C. I. Modant 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. Mordant 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. Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83, 84;
C. I. C. such as Mordant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53. I. Modant dye, C.I. I. C. such as Bat Green 1 I. Vat dye etc.

The following dyes may be mentioned.
Product names of BASF: Lumogen (registered trademark) Lumogen F Yellow 083, Lumogen (registered trademark) F Yellow 170, Lumogen (registered trademark) F Orange 240 and Lumogen (registered trademark) F Red 305.

As the pigment, known pigments can be used, and examples thereof include pigments classified into pigments by a color index (published by The Society of Dyers and Colorists). These may be used alone or in combination of two or more.
Specifically, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, Yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, 231;
C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and the like orange pigments;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 178, 179, 180, 190, 192, 209, 215, 216, 224, 242, 254, 255, 264, Red pigments such as 265, 266, 268, 269, 273;
C. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60 and other blue pigments;
C. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and the like violet color pigments;
C. I. Pigment Green 7, 36, 58, 59 and other green pigments;
C. I. Pigment Brown 23, 25 and other brown pigments;
C. I. Pigment Black 1, 7, 31, 32 and other black pigments.

Examples of the colorant (A1) include yellow dyes and yellow pigments (hereinafter, they may be collectively referred to as “yellow colorant”), green dyes and green pigments (hereinafter, these may be collectively referred to as “green colorant”). May be said), a yellow pigment and a green pigment are more preferable, and a green pigment is still more preferable.
The yellow dye includes dyes whose hue is classified as yellow among the above dyes, and the yellow pigments include pigments whose hue is classified as yellow among the above pigments.
Among the yellow pigments, a quinophthalone yellow pigment, a metal-containing yellow pigment and an isoindoline yellow pigment are preferable, and C.I. I. Pigment Yellow 129, 138, 139, 150, 185, 231 are more preferable, and C.I. I. Pigment Yellow 138, 139, 150, 185, 231 are more preferable.
Examples of the green dye include dyes whose hue is classified into green among the above dyes, and examples of green pigments include pigments whose hue is classified into green among the above pigments.
Among the green pigments, phthalocyanine pigments are preferable, and at least one selected from the group consisting of halogenated copper phthalocyanine pigments and halogenated zinc phthalocyanine pigments is more preferable, and C.I. I. Pigment Green 7, 36, 58 and 59 is more preferable.

The colorant (A1) is preferably a colorant containing at least one selected from a green colorant and a yellow colorant.

The colorant (A1) is, if necessary, a rosin treatment, a surface treatment using a derivative having an acidic group or a basic group introduced therein, a graft treatment with a polymer compound or the like on the surface of the colorant (A1), sulfuric acid. Atomization treatment by an atomization method or the like, a cleaning treatment by an organic solvent or water for removing impurities, a removal treatment of an ionic impurity by an ion exchange method, or the like may be performed. The particle size of the colorant (A1) is preferably substantially uniform.

When the coloring composition contains the colorant (A1), the upper limit of the content of the compound (I) in the colorant (A) is usually 1% by mass or more based on the total amount of the colorant (A), It is preferably 2% by mass or more, more preferably 10% by mass or more, further preferably 25% by mass or more, and particularly preferably 50% by mass or more. On the other hand, the upper limit of the content of the compound (I) in the colorant (A) is usually 100% by mass or less based on the total amount of the colorant (A).

When the coloring composition contains the coloring agent (A1), the content of the coloring agent (A) in the coloring composition is usually 0.1% by mass or more and 99% by mass or less with respect to the total amount of solids in the coloring composition. % Or less, for example, 0.1% by mass or more and 90% by mass or less, preferably 0.5% by mass or more and 80% by mass or less, and more preferably 0.7% by mass or more and 70% by mass or less. And particularly preferably 1% by mass or more and 60% by mass or less.

When the coloring composition contains the solvent (E), a colorant-containing liquid containing the compound (I) or the colorant (A) and the solvent (E) is prepared in advance, and then the colorant-containing liquid is used. Coloring compositions may be prepared. When the compound (I) or the colorant (A) is not dissolved in the solvent (E), the colorant-containing liquid is prepared by dispersing the compound (I) or the colorant (A) in the solvent (E) and mixing them. it can. The colorant-containing liquid may contain a part or all of the solvent (E) contained in the coloring composition.

The solid content in the colorant-containing liquid is preferably 0.01% by mass or more and 99.99% by mass or less, more preferably 0.1% by mass or more and 99.9% by mass based on the total amount of the colorant-containing liquid. % By mass or less, more preferably 0.1% by mass or more and 99% by mass or less, particularly preferably 1% by mass or more and 90% by mass or less, further preferably 1% by mass or more and 60% or less, still more preferably 3% by mass or more. It is from 50% by mass to 50% by mass, particularly preferably from 3% by mass to 30% by mass, and most preferably from 5% by mass to 30% by mass.

The content of the compound (I) or the colorant (A) in the colorant-containing liquid is usually 100% by mass or less, preferably 0.0001% by mass or more and 99% by mass in the total amount of solids in the colorant-containing liquid. 0.99 mass% or less, more preferably 0.01 mass% or more and 99 mass% or less, further preferably 1 mass% or more and 99 mass% or less, and particularly preferably 10 mass% or more and 99 mass% or less. It is more preferably 20% by mass or more and 99% by mass or less.
In the present specification, the “total amount of solids in the colorant-containing liquid” refers to the total amount of components excluding the solvent (E) from the colorant-containing liquid. The total amount of solid content and the content of each component relative thereto can be measured by a known analysis means such as liquid chromatography or gas chromatography.

The colorant (A1) can be made to be in a state in which the colorant (A1) is uniformly dispersed in the colorant (A1) -containing liquid by including a dispersant in the dispersion treatment. Each of the colorants (A1) may be subjected to a dispersion treatment alone or a mixture of a plurality of types may be subjected to a dispersion treatment.

Examples of the dispersant include surfactants, and any of cationic, anionic, nonionic and amphoteric surfactants may be used. Specific examples thereof include polyester-based, polyamine-based, and acrylic-based surfactants. You may use these dispersants individually or in combination of 2 or more types. As the dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Sols Perth (registered trademark) (manufactured by Zeneca Corporation), and EFKA (registered trademark) are trade names. (Manufactured by BASF Co., Ltd.), Azisper (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.) and Disperbyk (registered trademark) (manufactured by Big Chemie), BYK (registered trademark) (manufactured by Big Chemie), and the like. Can be mentioned.

When a dispersant is used to prepare the colorant-containing liquid, the amount of the dispersant (solid content) is usually 10,000 parts by mass or less based on 100 parts by mass of the compound (I) or the colorant (A). It is preferably 5000 parts by mass or less, more preferably 1000 parts by mass or less, further preferably 500 parts by mass or less, particularly preferably 300 parts by mass or less, and further preferably 100 parts by mass or less. It is more preferably 5 parts by mass or more and 100 parts by mass or less, and particularly preferably 5 parts by mass or more and 50 parts by mass or less. When the amount of the dispersant used is in the above range, a more uniformly dispersed colorant-containing liquid tends to be obtained.

[Resin (B)]
The resin (B) is preferably an alkali-soluble resin, and at least one monomer selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter referred to as “monomer (a)”). It is more preferable that the polymer has a structural unit derived from (in some cases).
The resin (B) is 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 A copolymer having the structural unit of is preferable.
As the other structural unit, a monomer copolymerizable with the monomer (a) (however, different from the monomer (a) and the monomer (b). Hereinafter, “monomer (c)”. In some cases), a structural unit having an ethylenically unsaturated bond, and the like.

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

The monomer (b) is a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of oxirane ring, oxetane ring and tetrahydrofuran ring) and an ethylenically unsaturated bond. Say. 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 oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “monomer (b1)”), an oxetanyl group and an ethylenically unsaturated bond. (Hereinafter sometimes referred to as “monomer (b2)”) and a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “monomer (b3)”) ) And the like.

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

As the monomer (b1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable.
Specific examples of the monomer (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, vinylbenzyl glycidyl ether, α- Methyl vinyl benzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxy) Methyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4 Examples thereof include 5-tris (glycidyloxymethyl) styrene and 2,4,6-tris (glycidyloxymethyl) styrene.
Examples of the monomer (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide (registered trademark) 2000; manufactured by Daicel Corp.), and 3,4-epoxycyclohexylmethyl. (Meth) acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer (registered trademark) M100; manufactured by Daicel) , A compound represented by the formula (BI), a compound represented by the formula (BII), and the like.

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

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

Examples of the alkyl group having a hydrogen atom substituted with hydroxy include, for example, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1 Examples thereof include -hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group and 4-hydroxybutyl group.

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

Examples of the alkanediyl group include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, Hexane-1,6-diyl group and the like can be mentioned.

X ^a and X ^b are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— and * —CH ₂ CH ₂ —O—, more preferably a single bond, * —CH ₂ CH ₂ —O— can be mentioned (* represents a bond with O).

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

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

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

As the monomer (b2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable.
Examples of the monomer (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3 -Acryloyloxymethyl oxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, etc. Is mentioned.

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

The monomer (b) is preferably the monomer (b1) from the viewpoint that the obtained color filter can have higher reliability such as heat resistance and chemical resistance. Further, the monomer (b1-2) is more preferable in that the storage stability of the coloring composition is excellent.

Examples of the monomer (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl. (Meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2. 1.0 ^2,6 ] Decan-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-9-yl (meth) acrylate, tricyclo [5.2.1.0 ^{2 , 6} ] decen-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decen-9-yl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) ) (Meth) acrylic acid esters such as acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate and benzyl (meth) acrylate;
Hydroxy group-containing (meth) acrylic acid ester such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2] .1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy -5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2 1.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5,6-bis (cyclohexyl) Bicyclo unsaturated compounds such as oxycarbonyl) bicyclo [2.2.1] hept-2-ene;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate and N- (9-acridinyl) maleimide;
Vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, vinyltoluene and p-methoxystyrene; vinyl group-containing nitriles such as (meth) acrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; (meth) acrylamide And vinyl group-containing amides such as vinyl acetate; esters such as vinyl acetate; dienes such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene;
Among these, styrene, vinyltoluene, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, tricyclo [5.2.1] from the viewpoint of copolymerization reactivity and heat resistance. .0 ^2,6 ] Decan-9-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6} ] Decen-9-yl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and benzyl (meth) acrylate are preferable.

The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth) acryloyl group. The resin having such a structural unit is a group having a monomer (a) or a monomer (b) in a polymer having a structural unit derived from the monomer (a) or the monomer (b). It can be obtained by adding a monomer having an ethylenically unsaturated bond to a group capable of reacting with.
Examples of such a structural unit include a structural unit obtained by adding glycidyl (meth) acrylate to a (meth) acrylic acid unit, a structural unit obtained by adding 2-hydroxyethyl (meth) acrylate to a maleic anhydride unit, and glycidyl (meth) ) A structural unit in which (meth) acrylic acid is added to an acrylate unit and the like can be mentioned. Moreover, when these structural units have a hydroxy group, the structural unit which further added the carboxylic acid anhydride is also mentioned as a structural unit which has an ethylenically unsaturated bond.

A polymer having a structural unit derived from the monomer (a) can be produced, for example, by polymerizing a monomer constituting the structural unit of the polymer in a solvent in the presence of a polymerization initiator. The polymerization initiator, the solvent and the like are not particularly limited, and those usually used in the art can be used. For example, as the polymerization initiator, an azo compound (2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) or the like) or an organic peroxide (benzoyl peroxide or the like) The solvent may be any solvent that can dissolve each monomer.

The obtained polymer may be used as it is after the reaction, or may be used as a concentrated or diluted solution, or as a solid (powder) obtained by a method such as reprecipitation. May be used.
If necessary, a reaction catalyst (for example, tris (dimethylaminomethyl) phenol or the like) between a carboxylic acid or a carboxylic acid anhydride and a cyclic ether, a polymerization inhibitor (for example, hydroquinone), or the like may be used.
Examples of the carboxylic acid anhydride include maleic anhydride, citraconic acid anhydride, itaconic acid anhydride, 3-vinylphthalic acid anhydride, 4-vinylphthalic acid anhydride, 3,4,5,6-tetrahydrophthalic acid anhydride, 1 2,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride and the like.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] Decyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid Copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide / 2-hydroxyethyl (meth) acrylate copolymer, 3,4-epoxytricyclo [5 2.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / vinyltoluene copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth ) Acrylate / (meth) acrylic acid / 2-ethylhexyl (meth) acrylate copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / tricyclo [5.2 .1.0 ^2,6 ] decenyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene Copolymers, benzyl (meth) acrylate / (meth) acrylic acid copolymers, styrene / (meth) acrylic acid copolymers and JP-A-9-106071, JP-A-2004-29518 and JP-A-2004 Resins and the like described in the respective publications of Japanese Patent No. 361455 can be mentioned.
Among them, 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 a combination of two or more kinds. In this case, the resin (B) is at least 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate. / (Meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide / 2-hydroxyethyl (Meth) acrylate copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / vinyltoluene copolymer, 3,4-epoxy It is preferable to contain one or more selected from tricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / 2-ethylhexyl (meth) acrylate copolymer.

The weight average molecular weight (Mw) in terms of polystyrene of the resin (B) is preferably 1,000 or more and 100,000 or less, more preferably 1,000 or more and 50,000 or less, and further preferably 1,000 or more. It is 30,000 or less, and particularly preferably 3,000 or more and 30,000 or less.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1 or more and 6 or less, more preferably 1.001 or more and 4 or less, and further preferably 1. It is 01 or more and 4 or less.

The acid value (solid content conversion value) of the resin (B) is preferably 10 mg-KOH / g or more and 300 mg-KOH / g or less, more preferably 20 mg-KOH / g or more and 250 mg-KOH / g or less, further preferably 20 mg. -KOH / g or more and 200 mg-KOH / g or less, particularly preferably 20 mg-KOH / g or more and 170 mg-KOH / g or less, more preferably 30 mg-KOH / g or more and 170 mg-KOH / g or less, particularly preferably 60 mg-KOH / G or more and 150 mg-KOH / g or less, very preferably 70 mg-KOH / g or more and 140 mg-KOH / g or less, and very preferably 70 mg-KOH / g or more and 135 mg-KOH / g or less. Here, the acid value is a value measured as an amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (B), and can be determined by, for example, titration using an aqueous potassium hydroxide solution.

The content of the resin (B) in the coloring composition may be, for example, 0.1% by mass or more and 99.9% by mass or less, and preferably 0.5% by mass, based on the total amount of solids in the coloring composition. Mass% or more and 99 mass% or less, more preferably 1 mass% or more and 95 mass% or less, further preferably 2 mass% or more and 90 mass% or less, particularly preferably 3 mass% or more and 80 mass% or less, and further preferably Is 5 mass% or more and 70 mass% or less, more preferably 7 mass% or more and 60 mass% or less, particularly preferably 10 mass% or more and 50 mass% or less, and very preferably 15 mass% or more and 40 mass% or less. % Or less.

When a colorant-containing liquid is prepared in advance and then the colorant-containing liquid of the present invention is prepared using the colorant-containing liquid, the colorant-containing liquid is a resin (B) described later contained in the colorant composition. Part or all, preferably part may be included in advance. By preliminarily containing the resin (B), the dispersion stability of the colorant-containing liquid can be further improved.

The content of the resin (B) in the colorant-containing liquid may be, for example, 10000 parts by mass or less, and preferably 5000 parts by mass or less, relative to 100 parts by mass of the compound (I) or the coloring agent (A). , More preferably 1000 parts by mass or less, further preferably 1 part by mass or more and 500 parts by mass or less, particularly preferably 5 parts by mass or more and 200 parts by mass or less, and further preferably 10 parts by mass or more and 100 parts by mass or less. Is.

<Colored curable resin composition>
The colored curable resin composition contains a colored composition, a polymerizable compound (C), a polymerization initiator (D), and a solvent (E).

The content of the solid content in the colored composition contained in the colored curable resin composition is appropriately adjusted according to the chromaticity, brightness, film thickness, etc. required when the colored curable resin composition is cured. Although not particularly limited, it may be, for example, 1% by mass or more and 99% by mass or less, preferably 1% by mass or more and 90% by mass or less, and more preferably based on the total amount of solids in the colored curable resin composition. Is 2 mass% or more and 80 mass% or less, more preferably 3 mass% or more and 70 mass% or less, particularly preferably 4 mass% or more and 60 mass% or less, and further preferably 5 mass% or more and 50 mass% or less. Or less, particularly preferably 6% by mass or more and 40% by mass or less, and very preferably 7% by mass or more and 30% by mass or less.

The content of the compound (I) in the colored curable resin composition is not particularly limited because it is appropriately adjusted according to the chromaticity, brightness, film thickness, etc. required when the colored curable resin composition is cured. In the total amount of solids in the colored curable resin composition, it may be, for example, 0.1% by mass or more and 99% by mass or less, preferably 1% by mass or more and 90% by mass or less, and more preferably 2% by mass. Or more and 80 mass% or less, more preferably 3 mass% or more and 70 mass% or less, particularly preferably 4 mass% or more and 60 mass% or less, more preferably 5 mass% or more and 50 mass% or less, It is particularly preferably 6% by mass or more and 40% by mass or less, and most preferably 7% by mass or more and 30% by mass or less.

In the present specification, the “total amount of solids in the colored curable resin composition” refers to the total amount of components excluding the solvent (E) from the colored curable resin composition. The total amount of solid content and the content of each component relative thereto can be measured by a known analysis means such as liquid chromatography or gas chromatography. The content of solids in the colored curable resin composition may be, for example, 0.01% by mass or more and 100% by mass or less, preferably 0.1% by mass, with respect to the total amount of the colored curable resin composition. Or more and 99.9% by mass or less, more preferably 0.1% by mass or more and 99% by mass or less, still more preferably 1% by mass or more and 90% by mass or less, and particularly preferably 1% by mass or more and 60% or less. It is preferably 3% by mass or more and 50% by mass or less, more preferably 3% by mass or more and 30% by mass or less, and particularly preferably 5% by mass or more and 30% by mass or less.

The coloring pattern or colored coating film described below formed from the colored curable resin composition may have an absorption maximum (λmax) in a wavelength range of 420 nm or more and 510 nm or less, and preferably in a wavelength range of 440 nm or more and 500 nm or less. It has an absorption maximum (λmax).
The absorption maximum (λmax) and the absorbance can be measured using, for example, a colorimeter (OSP-SP-200; manufactured by OLYMPUS).

[Polymerizable compound (C)]
The polymerizable compound (C) is a compound that can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and is, for example, a compound having a polymerizable ethylenic unsaturated bond, preferably It is a (meth) acrylic acid ester compound.

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

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

Above all, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl ) Isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, Examples thereof include caprolactone-modified pentaerythritol tetra (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate, and preferably dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

The weight average molecular weight of the polymerizable compound (C) is preferably 50 or more and 4000 or less, more preferably 50 or more and 3500 or less, still more preferably 50 or more and 3000 or less, and particularly preferably 150 or more and 2900 or less. And particularly preferably 250 or more and 1,500 or less.

The content of the polymerizable compound (C) may be, for example, 1% by mass or more and 99% by mass or less, preferably 2% by mass or more and 90% by mass, based on the total amount of solids in the colored curable resin composition. Or less, more preferably 3% by mass or more and 80% by mass or less, further preferably 4% by mass or more and 70% by mass or less, particularly preferably 5% by mass or more and 60% by mass or less, and further preferably 6% by mass or less. It is from 50% by mass to 50% by mass, and particularly preferably from 7% by mass to 40% by mass.

[Polymerization initiator (D)]
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include O-acyl oxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds and acylphosphine oxide compounds.

Examples of the O-acyl oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane- 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1- (4-phenylsulfanylphenyl)- 3-Cyclopentylpropan-1-one-2-imine, N-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropan-1-one-2-imine, 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-Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazol-3-yl] -3-cyclopentylpropan-1-imine and N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3- Examples thereof include cyclopentylpropan-1-one-2-imine. As the O-acyl oxime compound, commercially available products such as Irgacure OXE01, OXE02 (above manufactured by BASF Ltd.) and N-1919 (manufactured by ADEKA) may be used. Among them, O-acyl oxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane- At least one selected from the group consisting of 1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferable, and N-benzoyl Oxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine is more preferred.

Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1- Examples thereof include on and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one. As the alkylphenone compound, commercially available products such as Irgacure 369, 907, 379 (all manufactured by BASF Corp.) may be used.
Examples of the alkylphenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, Mention may also be made of 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxyacetophenone and benzyldimethyl ketal.

Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4. , 4 ′, 5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4, 4 ', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2 '-Bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, for example, JP-B-48-38403 and JP-A-62-174204). And a imidazole compound 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 triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl). -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl)- 1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methyl) And phenyl) ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine. ..

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

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

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

The content of the polymerization initiator (D) is, for example, 0.01% by mass or more and 40% by mass or less with respect to the total amount of all the resins (B) and the polymerizable compound (C) contained in the colored curable resin composition. It may be the following, preferably 0.1% by mass or more and 30% by mass or less.

[Polymerization initiation aid (D1)]
The polymerization initiation aid (D1) is a compound or a sensitizer used for promoting the polymerization of the polymerizable compound whose polymerization is initiated by the polymerization initiator. When the polymerization initiator auxiliary agent (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.

As the amine compound, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-Ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly called Michler's ketone), 4,4′-bis (diethylamino) benzophenone and 4,4′-bis ( Examples thereof include ethylmethylamino) benzophenone, and preferably 4,4′-bis (diethylamino) benzophenone. Further, as the amine compound, a commercially available product such as EAB-F (produced by Hodogaya Chemical Co., Ltd.) may be used.

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

As the carboxylic acid compound, phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

When these polymerization initiation aids (D1) are used, their content is, for example, 0.01% by mass or more and 40% by mass or less based on the total amount of the resin (B) and the polymerizable compound (C). Good, and preferably 0.1% by mass or more and 30% by mass or less.

[Solvent (E)]
The solvent (E) is, for example, an ester solvent (solvent containing -COO- and not -O- in the molecule), ether solvent (solvent containing -O- in the molecule, not -COO-), ether Ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- and not -COO-), alcohol solvent (containing OH in the molecule, -O-, -CO- and -COO--free solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.

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

As the ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl Examples thereof include ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole and methylanisole.

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

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

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

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

The content of the solvent (E) is usually 99.99% by mass or less, preferably 0.1% by mass or more and 99.9% by mass or less, and more preferably based on the total amount of the colored curable resin composition. Is 1 mass% or more and 99.9 mass% or less, more preferably 10 mass% or more and 99 mass% or less, particularly preferably 40 mass% or more and 99 mass% or less, and further preferably 50 mass% or more 97. The content is preferably not more than 70% by mass, particularly preferably not less than 70% by mass and not more than 97% by mass, and most preferably not less than 75% by mass and not more than 95% by mass.

The colored curable resin composition of the present invention is prepared by dispersing all or part of the compound (I) in all or part of the solvent (E) to prepare a colored dispersion, and then using this colored dispersion. You may prepare it.

The content of the solid content in the colored dispersion may be, for example, 0.01% by mass or more and 99.99% by mass or less, preferably 0.1% by mass or more and 99.9% by mass, based on the total amount of the colored dispersion. Mass% or less, more preferably 0.1 mass% or more and 99 mass% or less, further preferably 1 mass% or more and 90 mass% or less, more preferably 1 mass% or more and 60% or less, and It is preferably 3% by mass or more and 50% by mass or less, particularly preferably 3% by mass or more and 30% by mass or less, and very preferably 5% by mass or more and 30% by mass or less.

The content of the compound (I) in the colored dispersion may be, for example, 0.0001% by mass or more, preferably 0.01% by mass or more, and more preferably in the total amount of solids in the colored dispersion. Is 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, still more preferably 20% by mass or more, and particularly preferably 30% by mass or more. On the other hand, the upper limit of the content of the compound (I) in the colored dispersion is usually 100% by mass or less, for example 99% by mass or less, based on the total amount of solids in the colored dispersion.

When all or part of the compound (I) is dispersed in all or part of the solvent (E) to prepare a colored dispersion liquid, by adding all or part of the resin (B), The dispersion stability of the dispersion can be further improved. The content of the resin (B) in the colored dispersion may be, for example, 10000 parts by mass or less, preferably 5000 parts by mass or less, and more preferably 1000 parts by mass with respect to 100 parts by mass of the compound (I). Or less, more preferably 1 part by mass or more and 500 parts by mass or less, particularly preferably 5 parts by mass or more and 200 parts by mass or less, and further preferably 10 parts by mass or more and 100 parts by mass or less.

The compound (I) is, if necessary, rosin-treated, surface-treated with a derivative having an acidic group or a basic group introduced therein, graft-treated with a polymer compound or the like on the surface of the compound (I), and atomized with sulfuric acid. A pulverization treatment by a method or the like, a cleaning treatment by an organic solvent or water for removing impurities, a removal treatment by an ion exchange method for ionic impurities, or the like may be performed. The particle size of compound (I) is preferably substantially uniform.

The compound (I) can be uniformly dispersed in the colored dispersion liquid by containing a dispersant and performing a dispersion treatment. The compound (I) may be subjected to dispersion treatment alone, or a mixture of plural kinds thereof may be subjected to dispersion treatment.

Examples of the dispersant include surfactants, and any of cationic, anionic, nonionic and amphoteric surfactants may be used. Specific examples thereof include polyester-based, polyamine-based, and acrylic-based surfactants. You may use these dispersants individually or in combination of 2 or more types. As the dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Sols Perth (registered trademark) (manufactured by Zeneca Corporation), and EFKA (registered trademark) are trade names. (Manufactured by BASF Co., Ltd.), Azisper (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by Big Chemie Co., Ltd.), BYK (registered trademark) (manufactured by Big Chemie Co., Ltd.), etc. Can be mentioned.

When a dispersant is used, the amount of the dispersant (solid content) used is 10000 parts by mass or less, preferably 5000 parts by mass or less, and more preferably 1000 parts by mass with respect to 100 parts by mass of the compound (I). Or less, more preferably 500 parts by mass or less, particularly preferably 300 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 5 parts by mass or more and 100 parts by mass or less, particularly It is preferably 5 parts by mass or more and 50 parts by mass or less. When the amount of the dispersant used is within the above range, a colored dispersion liquid in a more uniform dispersed state tends to be obtained.

The colored curable resin composition of the present invention may further contain a leveling agent (F) and an antioxidant.

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

Examples of the fluorinated surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florade (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and F543. R30, RS-718-K (manufactured by DIC Corporation), F-Top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Examples thereof include S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratories, Inc.).

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

When the leveling agent (F) is contained, its content is usually 0.0005 mass% or more and 5 mass% or less, preferably 0.001 mass% or more 1 with respect to the total amount of the colored curable resin composition. Mass%, more preferably 0.001 mass% or more and 0.5 mass% or less, still more preferably 0.002 mass% or more and 0.2 mass% or less, and particularly preferably 0.005 mass% or more. It is 0.1 mass% or less. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

[Antioxidant]
From the viewpoint of improving the heat resistance and light resistance of the colorant, it is preferable to use the antioxidant alone or in combination of two or more kinds. The antioxidant is not particularly limited as long as it is an industrially commonly used antioxidant, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant and the like can be used.

Examples of the phenolic antioxidant include Irganox 1010 (Irganox 1010: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Corp.), Irganox 1076 (Irganox 1076: octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, manufactured by BASF Ltd.), Irganox 1330 (Irganox 1330: 3, 3 ', 3') ', 5,5', 5 ''-hexa-tert-butyl-a, a ', a' '-(mesitylene-2,4,6-triyl) tri-p-cresol, manufactured by BASF Ltd., Irganox 3114 (Irganox 3114: 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H ) -Trione, manufactured by BASF Corporation, Irganox 3790 (Irganox 3790: 1,3,5-tris ((4-tert-butyl-3-hydroxy-2,6-xylyl) methyl) -1,3,3) 5-triazine-2,4,6 (1H, 3H, 5H) -trione, manufactured by BASF Ltd., Irganox 1035 (Irganox 1035: thiodiethylenebis [3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate], manufactured by BASF Ltd., Irganox 1135 (Irganox 1135: benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl) Ester, manufactured by BASF Co., Ltd., Irganox 1520L (Irganox 1520L: 4,6-bis (octylthiomethyl) -o-cresol, manufactured by BASF Co., Ltd.), Irganox 3125 (Irganox 3125, manufactured by BASF Co., Ltd.) ), Irganox 565 (Irganox 565: 2,4-bis (n-octylthio) -6- (4-hydroxy3 ′, 5′-di-tert-butylanilino) -1,3,5-triazine, BASF (strain) )), Adekastab AO-80 (Adekastab AO-80: 3,9-bis (2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethyl Ethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, ADEKA Co., Ltd.), Sumilizer BHT (Sumilizer BHT, Sumitomo Chemical Co., Ltd.), Sumilizer GA-80 (Sumilizer GA-80, Sumitomo Chemical Co., Ltd.), Sumilizer GS (Sumilizer GS, Sumitomo Chemical Co., Ltd.) Cyanox 1790 (Cyanox 1790, manufactured by Cytec Co., Ltd.), vitamin E (manufactured by Eisai Co., Ltd.) and the like.

Examples of the phosphorus-based antioxidant include Irgafos 168 (Irgafos 168: tris (2,4-di-tert-butylphenyl) phosphite, manufactured by BASF Ltd.), Irgafos 12 (Irgafos 12: Tris [2- [[2,4,8,10-Tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine-6-yl] oxy] ethyl] amine, manufactured by BASF Corporation, Irgafos 38: bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid, manufactured by BASF Ltd., ADEKA STAB 329K (manufactured by ADEKA), ADEKA STAB PEP36 (manufactured by ADEKA), ADEKA STAB PEP-8 (manufactured by ADEKA), Sandstab P-EPQ (manufactured by Clariant), Weston 618 (Weston 618, manufactured by GE), Weston 619G (Weston 619G, GE). Company), Ultranox 626 (Ultranox 626, manufactured by GE) and Sumilizer GP (Sumilizer GP: 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4. 8,10-tetra-tert-butyldibenz [d, f] [1.3.2] dioxaphosphepine) (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

Examples of the sulfur-based antioxidants include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl or distearyl, and β-alkylmercaptopropiones such as tetrakis [methylene (3-dodecylthio) propionate] methane. Examples thereof include acid ester compounds.

[Other ingredients]
The colored curable resin composition of the present invention may optionally contain additives known in the art such as a filler, another polymer compound, an adhesion promoter, a light stabilizer and a chain transfer agent. ..
Examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycid. Xypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercapto Propyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-amino Propylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane and the like can be mentioned.

<Method for producing colored curable resin composition>
The colored curable resin composition includes, for example, a colorant (A), a resin (B), a solvent (E), a leveling agent (F), a polymerizable compound (C), and a polymerizable compound (C) when patterning by a photolithography method. It can be prepared by mixing with the polymerization initiator (D), the polymerization initiation aid (D1) and other components.
The pigment is preferably mixed with a part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, part or all of the pigment dispersant and the resin (B) may be blended, if necessary. The target colored curable resin composition can be prepared by mixing the remaining components in the pigment dispersion liquid thus obtained so as to have a predetermined concentration.
The dye may be dissolved in advance in a part or all of the solvent (E) to prepare a solution.
It is preferable to filter the solution with a filter having a pore size of 0.01 μm or more and 1 μm or less.
The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of 0.1 μm or more and 10 μm or less.

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

The film thickness of the color filter to be produced is not particularly limited and can be appropriately adjusted according to the purpose and application, and is, for example, 0.1 μm or more and 30 μm or less, preferably 0.1 μm or more and 20 μm or less, More preferably, it is 0.5 μm or more and 6 μm or less.

As the substrate, a glass plate, a resin plate, silicon, or a substrate on which aluminum, silver, a silver / copper / palladium alloy thin film or the like is formed is used. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

The formation of each color pixel by the photolithography method can be performed by a known or commonly used apparatus and conditions. For example, it can be manufactured as follows.
First, a colored curable resin composition is applied onto a substrate, and volatile components such as a solvent are removed by heating and drying (pre-baking) and / or reduced pressure drying, followed by drying to form a smooth colored curable resin composition layer. obtain.
Examples of the coating method include a spin coating method, a slit coating method, and a slit and spin coating method.

The temperature for heat drying is preferably 30 ° C. or higher and 120 ° C. or lower, and more preferably 50 ° C. or higher and 110 ° C. or lower. The heating time is preferably 10 seconds or more and 60 minutes or less, and more preferably 30 seconds or more and 30 minutes or less.
When drying under reduced pressure, it is preferable to perform drying under a pressure of 50 Pa or more and 150 Pa or less in a temperature range of 20 ° C. or more and 25 ° C. or less.
The film thickness of the colored curable resin composition is not particularly limited and may be appropriately selected according to the intended film thickness of the color filter.

Next, the colored curable resin composition layer is exposed through a photomask for forming an intended colored pattern. An exposure apparatus such as a mask aligner and a stepper can be provided because it is possible to uniformly illuminate parallel light rays on the entire exposed surface and to perform accurate alignment between the photomask and the substrate on which the colored curable resin composition layer is formed. Is preferably used.

As a light source used for exposure, a light source that emits light having a wavelength of 250 nm or more and 450 nm or less may be used. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light of about 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. You may. Specific examples thereof include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.

A colored pattern is formed on the substrate by bringing the colored curable resin composition layer after exposure into contact with a developer to develop the layer. By the development, the unexposed portion of the colored curable resin composition layer is dissolved in the developer and removed.
As the developing solution, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate and tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution may be, for example, 0.01% by mass or more and 10% by mass or less. Furthermore, the developing solution may contain a surfactant.
The developing method may be a paddle method, a dipping method, a spray method or the like. Further, the substrate may be tilted at an arbitrary angle during development.
The substrate after development is preferably washed with water.
Furthermore, it is preferable to perform post-baking on the obtained colored pattern.

The color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor, and particularly as a color filter used in a liquid crystal display device.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples as well as the present invention, and may be appropriately modified within a range compatible with the gist of the preceding and the following. Of course, it is possible to carry out, and all of them are included in the technical scope of the present invention. In the following, "part" means "part by mass" and "%" means "% by mass" unless otherwise specified.

In the following examples, the structures of compounds were confirmed by mass spectrometry (LC: 1200 type manufactured by Agilent, MASS; LC / MSD6130 type manufactured by Agilent).

The polystyrene equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.
Device: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Solid concentration of analytical sample: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector: RI
Calibration standard substance: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The polystyrene equivalent weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was taken as the dispersity.

<Preparation of Compound I-1>
8.0 parts of 3,4,9,10-perylenetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 80 parts of water were mixed. While maintaining the temperature of the obtained mixture at 60 ° C, 8.0 parts of potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at 60 ° C for 6 hours. While maintaining the temperature of the obtained mixture at 5 ° C. or lower, 263 parts of prediluted sulfuric acid (7.4 parts of concentrated sulfuric acid and 256 parts of water) was added to produce an orange precipitate. The mixture containing the orange precipitate was filtered, and the residue after filtration was washed with 300 parts of water and 300 parts of methanol. The resulting residue was dried under reduced pressure at 60 ° C. to obtain 6.1 parts of the compound I-1 represented by the formula (I-1) (yield 70%).

<Identification of Compound I-1>
(Mass Spectrometry) ionization mode = ESI-: m / z = [ M-H] - 427
Exact Mass: 428

<Preparation of Compound I-2>
Mix 3,4,9,10-perylenetetracarboxylic dianhydride (Tokyo Chemical Industry Co., Ltd.) 10 parts, potassium hydroxide 6.4 parts (Wako Pure Chemical Industries, Ltd.), water 57 parts did. The temperature of the resulting mixture was heated to 100 ° C. and stirred for 6 hours. While maintaining the temperature of the obtained mixture at 5 ° C or lower, 1000 parts of acetone was added. The obtained mixture was filtered, and the residue after filtration was washed 3 times with 25 parts of acetone. The obtained residue was dried under reduced pressure at 60 ° C. to obtain 12 parts of compound I-2a represented by the formula (I-2a) (yield 80%).

1.2 parts of the compound represented by the compound (1-2a) and 103 parts of water were added and dissolved. At 23 ° C., 0.98 parts of magnesium acetate tetrahydrate and 227 parts of water were added dropwise, and the mixture was stirred at 23 ° C. for 6 hours, whereupon a red precipitate was formed. The mixture containing the red precipitate was filtered, and the residue after filtration was washed 3 times with 1 part of water. The obtained residue was dried under reduced pressure at 60 ° C. to obtain 0.24 part of compound I-2 represented by the formula (I-2) (yield 25%).

<Preparation of Compound I-3>
Synthesis was performed in the same manner as in Example 2 except that 1.2 parts of barium acetate was added dropwise instead of 0.98 part of magnesium acetate tetrahydrate added in Example 2. The precipitate obtained by the dropwise addition of 1.2 parts of barium acetate was also red. 1.3 parts of compound I-3 represented by the formula (I-3) was obtained (yield 91%).

<Preparation of Compound I-4>
Diisobutyl 3,9-perylenedicarboxylate (Solvent Green 5, manufactured by Tokyo Chemical Industry Co., Ltd.) 10 parts, potassium hydroxide 2.8 parts (Wako Pure Chemical Industries, Ltd.), water 28 parts were mixed to obtain 100 The mixture was stirred at C for 15 hours. While maintaining the temperature of the obtained mixture at 5 ° C. or lower, 6.2 parts of concentrated sulfuric acid was added, and a yellow precipitate was produced. The mixture containing this yellow precipitate was filtered, and the residue after filtration was washed 3 times with 100 parts of water. The obtained residue was dried under reduced pressure at 60 ° C. to obtain 6.2 parts of compound I-4 represented by the formula (I-4) (yield 83%).

<Identification of Compound I-4>
(Mass Spectrometry) ionization mode = ESI-: m / z = [ M-H] - 339
Exact Mass: 340

<Preparation of Compound I-5>
3.5 parts of diisobutyl 4,10-dicyanoperylene-3,9-dicarboxylate (Lumogen (registered trademark) F Yellow 083, manufactured by BASF Ltd.) and 1.6 parts of sodium hydroxide (Wako Pure Chemical Industries, Ltd.) Manufactured) and 35 parts of water were mixed and stirred at 100 ° C. for 10 hours. While maintaining the temperature of the obtained mixture at 5 ° C. or lower, 5.2 parts of concentrated hydrochloric acid was added to produce an orange precipitate. The mixture containing the orange precipitate was filtered, and the residue after filtration was washed 3 times with 100 parts of water.
The obtained residue was dried under reduced pressure at 60 ° C. to obtain 2.6 parts of compound I-5 represented by the formula (I-5) (yield 93%).

<Identification of Compound I-5>
(Mass Spectrometry) ionization mode = ESI-: m / z = [ M-H] - 389
Exact Mass: 390

Synthesis example 1
An appropriate amount of nitrogen was flown into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80 ° C. with stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] A mixed solution of 289 parts of a mixture of decan-9-yl acrylate (content ratio is 1: 1 in molar ratio) and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a 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 dropping, the mixture was kept at 80 ° C. for 4 hours, then cooled to room temperature, solid content 35.1%, copolymer (resin B1) solution having a viscosity of 125 mPa · s measured by a B-type viscometer (23 ° C.). Got The weight average molecular weight Mw of the produced copolymer was 9.2 × 10 ³ , the dispersity was 2.08, and the acid value in terms of solid content was 77 mg-KOH / g. The resin B1 has the following structural units.

Example 1
(1) Preparation of Coloring Composition Each component was mixed in the following proportions, and the coloring agent was dispersed using a bead mill to obtain a coloring composition 1.
Colorant: Compound I-1 50 parts;
Dispersant: BYK-LPN6919 (manufactured by BYK Japan KK) 58 parts; Resin (B): Resin B1 solution 93 parts; Solvent (E): Propylene glycol monomethyl ether acetate 800 parts

Then, the respective components were mixed in the following proportions to obtain a colored curable resin composition 1.
Coloring composition 1 400 parts;
Resin (B): Resin B1 solution 45 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 25 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Ltd.) 15 parts;
Solvent (E): Propylene glycol monomethyl ether acetate 86 parts;
Leveling agent: polyether modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.12 parts

(2) Preparation of colored coating film A 5 cm square glass substrate (Eagle XG; manufactured by Corning Incorporated) was spin-coated with a colored curable resin composition so that the film thickness after post-baking would be 1.7 to 2 μm. And then prebaked at 100 ° C. for 3 minutes to form a colored curable resin composition layer. After allowing to cool, the colored curable resin composition layer formed on the substrate was exposed to 80 mJ / cm ^{2 in} an air atmosphere by using an exposure device (TME-150RSK; manufactured by Topcon Corp.) (based on 365 nm). ). After the light irradiation, post-baking was performed in an oven at 230 ° C. for 30 minutes to obtain a colored coating film.

(3) Heat resistance test The absorbance of the obtained colored coating film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). The colored coating film after the measurement was further heated in an oven in an air atmosphere at 230 ° C. for 120 minutes, and then the absorbance was measured with a colorimeter. The absorbance retention was determined from the absorbance change of the maximum absorption wavelength of the colored curable composition film before and after the heat resistance test.

(4) Light resistance test An ultraviolet cut filter (COLORED OPTICAL GLASS L38; manufactured by Hoya Co., Ltd., which cuts light of 380 nm or less) is arranged on the obtained colored coating film, and a light resistance tester (SUNTEST CPS +: Toyo Seiki Co., Ltd.) is arranged. (Manufactured by K.K.) and irradiated with xenon lamp light for 48 hours, and then the absorbance was measured with a colorimeter. The absorbance retention was determined from the change in absorbance at the maximum absorption wavelength of the colored coating film before and after the light resistance test.

Examples 2-5 and Comparative Example 1
Instead of 50 parts of the compound (I-1) as a colorant,
50 parts of compound (I-2) (Example 2),
50 parts of compound (I-3) (Example 3),
50 parts of compound (I-4) (Example 4),
50 parts of compound (I-5) (Example 5),
50 parts of Solvent Green 5 (manufactured by Tokyo Chemical Industry Co., Ltd.) (Comparative Example 1)
The same as Example 1 except that was used. The results are shown in Table 2.

Claims

A coloring composition comprising a compound represented by the following formula (I) and a resin.

[In the formula,
R 1 to R 3 each independently represent a hydrogen atom, —CO 2 — , a halogen atom, a cyano group, a nitro group, or a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.
R 4 to R 11 are, independently of each other, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a hydrogen atom, a halogen atom, cyano. group, a nitro group, -CO 2 -, or -S (O) 2 O - represents a.
-CH 2- which is contained in the hydrocarbon group having 1 to 40 carbon atoms and may have a substituent represented by R 4 to R 11 and does not form a ring, and R 4 to R 11 The —CH 2 — contained in the heterocyclic group which may have a substituent and does not form a ring is —O—, —CO—, —S (O) 2 —, —NR x1 —. May be replaced with. However, -COOH and -S (O) 2 OH are not formed by replacing -CH 2- .
R x1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
M x + represents a hydron or an x-valent metal cation.
x represents an integer of 2 or more.
a represents the valence of the structure in parentheses with a, and represents an integer of 1 or more and 12 or less.
b represents the number of M X + and represents an integer of 1 or more and 12 or less.
a and b are the following formulas:
a = bx
Meet ]
A colored curable resin composition containing the colored composition according to claim 1, a polymerizable compound, a polymerization initiator, and a solvent.
A color filter formed from the colored curable resin composition according to claim 2.
A display device including the color filter according to claim 3.