CN113056523B

CN113056523B - coloring composition

Info

Publication number: CN113056523B
Application number: CN201980074257.2A
Authority: CN
Inventors: 滨木裕史; 冈本信之
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2018-11-13
Filing date: 2019-11-11
Publication date: 2023-08-22
Anticipated expiration: 2039-11-11
Also published as: KR20210088554A; TWI811481B; JP2020079397A; CN113056523A; TW202024079A; WO2020100783A1; JP7412141B2

Abstract

The invention aims to provide a coloring composition with excellent heat resistance. The present invention relates to a coloring composition comprising a colorant and a resin, wherein the colorant comprises a compound represented by formula (I) and a fluorescent dye, and the fluorescent dye comprises a compound having a structure different from that of the compound represented by formula (I).

Description

Coloring composition

Technical Field

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

Background

In the field of organic semiconductor materials, a material containing a perylene tetracarboxylic diimide compound is known (patent document 1).

Prior art literature

Patent literature

Patent document 1: international publication No. 2011/105152

Disclosure of Invention

In the field of colorants, a colorant containing a fluorescent dye has been used, and in a coloring composition containing such a colorant, improvement in heat resistance has been demanded.

The purpose of the present invention is to provide a coloring composition with excellent heat resistance.

The invention provides a coloring composition, a coloring curable resin composition, a color filter and a display device.

[1] A coloring composition comprising a colorant and a resin, wherein the colorant comprises a compound represented by the following formula (I) and a fluorescent dye, and the fluorescent dye comprises a compound having a structure different from that of the compound represented by the formula (I).

In the formula (I) of the formula (I),

R ¹ ～R ⁴ each independently represents an alkyl group having 5 to 10 carbon atoms.

R ⁵ ～R ¹² Each independently represents a hydrocarbon group having 1 to 40 carbon atoms, a hydrogen atom, a halogen atom or a nitro group which may have a substituent.]

[2] The coloring composition according to [1], wherein the compound having a structure different from that of the compound represented by the above formula (I) is a red fluorescent dye.

[3] The coloring composition according to [1] or [2], wherein the red fluorescent dye is a compound represented by the following formula (II).

In the formula (II),

Ar ¹ ～Ar ⁶ each independently represents an aryl group which may have a substituent.

R ¹⁵ ～R ¹⁸ Each independently represents a hydrocarbon group having 1 to 40 carbon atoms, a hydrogen atom, a halogen atom or a nitro group which may have a substituent.]

[4] A colored curable resin composition comprising a compound represented by the following formula (I), a fluorescent dye, a resin, a polymerizable compound, a polymerization initiator and a solvent.

In the formula (I) of the formula (I),

[5] A color filter formed from the colored curable resin composition according to [4 ].

[6] A display device comprising the color filter of [5 ].

According to the present invention, a coloring composition having excellent heat resistance can be provided.

Detailed Description

(1) Coloring composition

The coloring composition of the present invention contains a colorant (hereinafter, also referred to as a colorant (a)) and a resin (hereinafter, also referred to as a resin (B)).

The colorant (a) contains a compound represented by the formula (I) (hereinafter, also referred to as compound (I)) and a fluorescent dye (hereinafter, also referred to as fluorescent dye (a)).

The fluorescent dye (a) contains a compound having a structure different from that of the compound represented by the formula (I). The structurally different compounds refer to compounds having different structures (chemical structures) when represented by the chemical formulas are preferable.

The compound having a structure different from that of the compound represented by the formula (I) may be, for example, a red fluorescent dye.

The red fluorescent dye may be, for example, a compound represented by formula (II) (hereinafter, also referred to as compound (II)).

The colorant (a) may contain a colorant other than the compound (I) and the fluorescent dye (a) (hereinafter, also referred to as a colorant (A1)).

The colorant (a) may contain 1 or 2 or more colorants (A1).

The coloring composition may contain a solvent (hereinafter, also referred to as a solvent (E)).

The compound (I) and the compound (II) may be dispersed in the solvent (E).

< Compound (I) >)

R ¹ ～R ⁴ The alkyl group has 5 to 10 carbon atoms, preferably 5 to 8 carbon atoms. R is R ¹ ～R ⁴ The alkyl group may be linear, branched or cyclic, and is preferably linear.

As R ¹ ～R ⁴ Examples of the straight-chain alkyl group include n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group. Among them, preferred are n-pentyl, n-hexyl, n-heptyl and n-octyl, and more preferred are n-pentyl and n-hexyl. These groups are preferable from the viewpoints of solubility in a solvent and fluorescence intensity.

As R ¹ ～R ⁴ Examples of the branched alkyl group include 1-methylbutyl, 1-methylpentyl, 1-methylhexyl, 1-methylheptyl, 1-methyloctyl, 1-methylnonyl, 1-ethylpropyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylhexyl, 1-ethylheptyl, 1-ethyloctyl, 2-methylbutyl, 2-methylpentyl, 2-methylhexyl, 2-methylheptyl, 2-methyloctyl, 2-methylnonyl, 2-ethylpropyl, 2-ethylbutyl, 2-ethylpentyl, 2-ethylhexyl, 2-ethylheptyl, 2-ethyloctyl, and the like.

As R ¹ ～R ⁴ Examples of the cyclic alkyl group include cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl Cyclononyl, cyclodecyl, and the like.

R ¹ ～R ⁴ For example, each of the groups may be independently a combination of a linear alkyl group and a cyclic alkyl group, or a combination of a branched alkyl group and a cyclic alkyl group. The number of carbon atoms of the group obtained by combining these may be 5 to 10.

R ¹ ～R ⁴ The same species or different species, preferably the same species.

As R ¹ ～R ⁴ Specific examples of (a) include groups represented by the following formulas. * Represents the bonding site.

As R ⁵ ～R ¹² Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, fluorine atoms and chlorine atoms are preferable.

As R ⁵ ～R ¹² Examples of the hydrocarbon group having 1 to 40 carbon atoms include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be saturated or unsaturated, or may be chain-shaped or cyclic.

As R ⁵ ～R ¹² Examples of the saturated or unsaturated chain aliphatic hydrocarbon group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, tetracosyl, tricosyl, tetracosyl, pentatriacontyl, hexatriacontyl, hexacosyl, and mixtures thereof, Linear alkyl groups such as a triacontanyl group, and a forty-alkyl group; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, (2-ethyl) butyl, isopentyl, neopentyl, tert-pentyl, (1-methyl) pentyl, (2-methyl) pentyl, (1-ethyl) pentyl, (3-ethyl) pentyl, (5-methyl) hexyl, (2-ethyl) hexyl and (3-ethyl) heptyl; alkenyl groups such as vinyl, 1-propenyl, 2-propenyl (allyl), (1-methyl) vinyl, 2-butenyl, 3-butenyl, 1, 3-butadienyl, (1- (2-propenyl)) vinyl, (1, 2-dimethyl) propenyl, and 2-pentenyl; etc. The number of carbon atoms of the saturated or unsaturated chain hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 15, particularly preferably 1 to 10. 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.

As R ⁵ ～R ¹² A saturated or unsaturated alicyclic hydrocarbon group represented by formula (I), examples thereof include cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1, 2-dimethylcyclohexyl, 1, 3-dimethylcyclohexyl, 1, 4-dimethylcyclohexyl, 2, 3-dimethylcyclohexyl, 2, 4-dimethylcyclohexyl, 2, 5-dimethylcyclohexyl 2, 6-dimethylcyclohexyl, 3, 4-dimethylcyclohexyl, 3, 5-dimethylcyclohexyl, 2-dimethylcyclohexyl, 3-dimethylcyclohexyl, 4-dimethylcyclohexyl, cyclooctyl cycloalkyl groups such as 2,4, 6-trimethylcyclohexyl, 2, 6-tetramethylcyclohexyl, 3, 5-tetramethylcyclohexyl, 4-pentylcyclohexyl, 4-octylcyclohexyl, and 4-cyclohexylcyclohexyl; cyclohexenyl (e.g., cyclohexane-2-ene, cyclohexane-3-ene), cycloheptene, cyclooctene, and the like; norbornyl, adamantyl, bicyclo [2.2.2 ]Octyl, and the like. The number of carbon atoms of the saturated or unsaturated alicyclic hydrocarbon group is preferably 3 to 30, more preferably 3 to 20, further preferably 4 to 20, particularly preferably 4 to 15, further preferably 5 to 15, particularly preferably 5 to 10. Of these, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctane are most preferredA base.

As R ⁵ ～R ¹² Examples of the aromatic hydrocarbon group include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl 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-butylphenyl group, trimethylphenyl 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-trimethyl-2-pentylphenyl group), 1-naphthyl group, 2-naphthyl group, 5,6,7, 8-tetrahydro-1-naphthyl group, 5,6,7, 8-tetrahydro-2-naphthyl group, 4-ethylphenyl group, 4-dodecylphenyl group, and the like. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 15.

R ⁵ ～R ¹² The hydrocarbyl group represented by the above may be a group obtained by combining 2 or more of the above-mentioned hydrocarbyl groups, and for example, an aromatic hydrocarbyl group may be a group obtained by combining an aromatic hydrocarbyl group with at least one of a chain hydrocarbyl group and an alicyclic hydrocarbyl group, and examples thereof include aralkyl groups such as benzyl group, phenethyl group, 1-methyl-1-phenylethyl group, and the like; aryl alkenyl groups such as phenyl vinyl (phenyl vinyl); aryl alkynyl groups such as phenyl ethynyl; phenyl groups having 1 or more phenyl groups bonded thereto, such as biphenyl and terphenyl; cyclohexylmethylphenyl, benzyl phenyl, (dimethyl (phenyl) methyl) phenyl, and the like.

R ⁵ ～R ¹² The hydrocarbon group represented may be a group obtained by combining 2 or more hydrocarbon groups as mentioned above, for example, a group obtained by combining a chain hydrocarbon group with an alicyclic hydrocarbon group, and examples thereof include cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, 2-methylAlkyl groups having 1 or more alicyclic hydrocarbon groups bonded thereto, such as cyclohexylmethyl, cyclohexylethyl, and adamantylmethyl.

The number of carbon atoms of the group obtained by combining 2 or more of the above hydrocarbon groups is preferably 4 to 30, more preferably 4 to 20, still more preferably 4 to 15, still more preferably 6 to 15.

As R ⁵ ～R ¹² Examples of the substituent which the hydrocarbon group having 1 to 40 carbon atoms may have include a halogen atom, a formyl group, a carboxyl group, a formyloxy group, a hydroxyl group, a thiol group, a sulfo group, a sulfamoyl group, a pentafluorosulfanyl group, a carbamoyl group, an amino group, a nitro group, a cyano group and, -COR ¹² 、－COOR ¹³ 、－OCOR ¹³ 、－OR ¹³ 、－SR ¹³ 、－SOR ¹³ 、－SO ₂ R ¹³ 、－SO ₂ NHR ¹³ 、－SO ₂ NR ¹³ R ¹⁴ 、－CONHR ¹³ 、－CONR ¹³ R ¹⁴ 、－NHR ¹³ 、－NR ¹³ R ¹⁴ 、－NHCOR ¹³ 、－NR ¹⁴ COR ¹³ Etc.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, fluorine atoms and chlorine atoms are preferable.

R ¹³ And R is ¹⁴ Each independently represents an alkyl group, a phenyl group or a naphthyl group.

R ¹³ And R is ¹⁴ The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5.

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

as-COR ¹³ Examples of the compound include acetyl, propionyl, butyryl, 2-dimethylpropionyl, pentanoyl, hexanoyl, (2-ethyl) hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl and undecanoyl A group, a dodecanoyl group, a heneicosanoyl group, a benzoyl group, and the like.

as-COOR ¹³ Examples thereof include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, (2-ethyl) hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, undecyloxycarbonyl, dodecyloxycarbonyl, phenoxycarbonyl, and eicosyloxycarbonyl.

as-OCOR ¹³ Examples thereof include acetoxy, propionyloxy, butyryloxy, 2-dimethylpropionoyloxy, pentanoyloxy, hexanoyloxy, (2-ethyl) hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy, decanoyloxy, undecanoyloxy, dodecanoyloxy, heneicosanoyloxy, benzoyloxy, vinylcarbonyloxy, and 2-propenyl carbonyloxy.

as-OR ¹³ Examples thereof include methoxy, ethoxy, propoxy, butoxy, pentyloxy, phenoxy, naphthyloxy and the like.

as-SR ¹³ Examples thereof include methylsulfanyl, ethylsulfanyl, propylsulfanyl, butylsulfanyl, tert-butylsulfanyl, pentylthanyl, hexylsulfanyl, (2-ethyl) hexylsulfanyl, heptylsulfanyl, octylsulfanyl, nonylsulfanyl, decylsulfanyl, undecylsulfanyl, dodecylsulfanyl, eicosyl, phenylsulfanyl and o-tolylsulfanyl.

as-SOR ¹³ Examples thereof include methylsulfinyl, ethylsulfinyl, propylsulfinyl, butylsulfinyl, pentylsulfinyl, phenylsulfinyl, naphthylsulfinyl and the like.

as-SO ₂ R ¹³ Examples thereof include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, pentylsulfonyl, phenylsulfonyl, and naphthylsulfonyl.

as-SO ₂ NHR ¹³ Examples thereof include N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl and N-isopropylsulfamoylAlkylsulfamoyl, N-butylsulfamoyl, N-isobutylsulfamoyl, N-sec-butylsulfamoyl, N-tert-butylsulfamoyl, N-pentylsulfamoyl, N- (1-ethylpropyl) sulfamoyl, N-hexylsulfamoyl, N- (2-ethyl) hexylsulfamoyl, N-heptylsulfamoyl, N-octylsulfamoyl, N-nonylsulfamoyl, N-decylsulfamoyl, N-undecylsulfamoyl, N-dodecylsulfamoyl, N-eicosylsulfamoyl, N-phenylsulfamoyl and the like.

as-SO ₂ NR ¹³ R ¹⁴ Examples thereof include N, N-dimethyl sulfamoyl, N-ethyl methyl sulfamoyl, N-diethyl sulfamoyl, N, N-propylmethylsulfamoyl, N-dipropylsulfamoyl, N-isopropylmethylsulfamoyl, N-diisopropylsulfamyl, N, N-tert-butylmethylsulfamoyl, N-diisobutylsulfamoyl, N-di-sec-butylsulfamoyl, N-di-tert-butylsulfamoyl, N-dibutylsulfamoyl, N-dipentylsulfamoyl, N, N-di (1-ethylpropyl) sulfamoyl, N-dihexylsulfamoyl, N-di (2-ethyl) hexylsulfamoyl, N, N-diheptylsulfamoyl, N-octylmethylsulfamoyl, N-dioctylsulfamoyl, N-dinonylsulfamoyl, N, N-decyl methylsulfamoyl, N-undecyl methylsulfamoyl, N-dodecyl methylsulfamoyl, N-eicosyl methylsulfamoyl, N-phenyl methylsulfamoyl, N-diphenyl sulfamoyl, and the like.

as-CONHR ¹³ Examples of the "N-methylcarbamoyl" group include "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 and "N-undecane" N-ethylcarbamoyl "groupAlkylcarbamoyl, N-dodecylcarbamoyl, N-eicosylcarbamoyl, N-phenylcarbamoyl, and the like.

as-CONR ¹³ R ¹⁴ Examples thereof include N, N-dimethylcarbamoyl, N-ethylmethylcarbamoyl, N-diethylcarbamoyl, N, N-propylmethylcarbamoyl, N-dipropylcarbamoyl, N-isopropylmethylcarbamoyl, N-diisopropylcarbamoyl, N, N-propylmethylcarbamoyl, N-dipropylcarbamoyl, N, N-isopropylmethylcarbamoyl, N-diisopropylcarbamoyl, N, N-dipentylcarbamoyl, N-di (1-ethylpropyl) carbamoyl, N-dihexylcarbamoyl, N, N-di (2-ethyl) hexylcarbamoyl, N-diheptylcarbamoyl, N-octylmethylcarbamoyl, N-dioctylcarbamoyl, N, N-di (2-ethyl) hexylcarbamoyl, N-diheptylcarbamoyl, N, N-octylmethylcarbamoyl, N-dioctylcarbamoyl, N.

as-NHR ¹³ Examples thereof include N-methylamino, N-ethylamino, N-propylamino, N-isopropylamino, N-butylamino, N-isobutylamino, N-sec-butylamino, N-tert-butylamino, N-pentylamino, N-hexylamino, N- (2-ethyl) hexylamino, N-heptylamino, N-octylamino, N-nonylamino, N-decylamino, N-undecylamino, N-dodecylamino, N-eicosylamino, N-phenylamino and the like.

as-NR ¹³ R ¹⁴ Examples thereof include N, N-dimethylamino, N-ethylmethylamino, N-diethylamino, N-propylmethylamino, N-dipropylamino, N, N-isopropylmethylamino, N-diisopropylamino, N-tert-butylmethylamino, N-diisobutylamino, N-di-sec-ondButylamino, N-di-tert-butylamino, N-butylmethylamino, N-dibutylamino, N-dipentylamino, N, N-di (1-ethylpropyl) amino, N-dihexylamino, N-di (2-ethyl) hexylamino, N-diheptylamino, N, N-dioctylamino, N-dinonylamino, N-decylmethylamino, N-undecylmethylamino, N, N-dodecylmethylamino, N-eicosylmethylamino, N-phenylmethylamino, N-diphenylamino and the like.

as-NHCOR ¹³ Examples thereof include acetylamino, propionylamino, butyrylamino, 2-dimethylpropionylamino, pentanoylamino, hexanoylamino, (2-ethyl) hexanoylamino, heptanoylamino, octanoylamino, nonanoylamino, decanoylamino, undecanoylamino, dodecanoylamino, heneicosanoylamino, benzoylamino and the like.

as-NR ¹⁴ COR ¹³ Examples thereof include N-methyl-N-acetylamino group and the like.

R ⁵ ～R ¹² Represented by-CH which is contained in a hydrocarbon group having 1 to 40 carbon atoms and does not form a ring ₂ Can be substituted by-O-, -CO-, -S (O) ₂ －、－NR ^x1 -. Wherein, -CH ₂ -not by substitution to 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, ethyl, n-propyl, n-butyl, n-pentyl, isopropyl, isobutyl, sec-butyl, and isopentyl groups.

As R ⁵ ～R ¹² Examples thereof include groups represented by the following formulas. * Represents the bonding site.

As R ⁵ ～R ¹² Preferred radicals are hydrogen, halogen, hydroxy, nitro, cyano, -CH ₃ The groups represented by the formulae (D-1) to (D-18), (E-1) to (E-27), (F-1) to (F-18) and (G-1) to (G-27). From the viewpoint of fluorescence intensity, R ⁵ ～R ¹² Preferably a hydrogen atom.

Specific examples of the compound (I) include compounds shown in table 1 below.

TABLE 1

R ¹

R ²

R ³

R ⁴

R ⁵

R ⁶

R ⁷

R ⁸

R ⁹

R ¹⁰

R ¹¹

R ¹²

I-1

(A-1)

H

I-2

(A-2)

H

I-3

(A-3)

H

I-4

(A-4)

H

I-5

(A-5)

H

I-6

(A-6)

H

I-7

(A-1)

(A-2)

(A-1)

(A-2)

H

I-8

(A-1)

(A-3)

(A-1)

(A-3)

H

I-9

(A-1)

(A-4)

(A-1)

(A-4)

H

I-10

(A-1)

(A-5)

(A-1)

(A-5)

H

I-11

(A-1)

(A-6)

(A-1)

(A-6)

H

I-12

(A-2)

(A-3)

(A-2)

(A-3)

H

I-13

(A-2)

(A-4)

(A-2)

(A-4)

H

I-14

(A-2)

(A-5)

(A-2)

(A-5)

H

I-15

(A-2)

(A-6)

(A-2)

(A-6)

H

I-16

(A-3)

(A-4)

(A-3)

(A-4)

H

I-17

(A-3)

(A-5)

(A-3)

(A-5)

H

I-18

(A-3)

(A-6)

(A-3)

(A-6)

H

I-19

(A-4)

(A-5)

(A-4)

(A-5)

H

I-20

(A-4)

(A-5)

(A-4)

(A-6)

H

I-21

(A-5)

(A-6)

(A-5)

(A-6)

H

Among them, the compounds (I-1) and (I-2) are preferable. These compounds tend to have high solubility in solvents and high fluorescence intensity.

As a preferred embodiment of the compound (I) in the present invention, there may be mentioned a compound represented by the following formula (I-1) (hereinafter, also referred to as compound (I-1)).

As another preferred embodiment of the compound (I) in the present invention, a compound represented by the following formula (I-2) (hereinafter, also referred to as compound (I-2)) is exemplified.

The compound (I) can be produced, for example, by reacting a compound represented by the following formula (pt 1) with a compound represented by the following formula (n 1) in a solvent.

[ formula, R ⁵ ～R ¹² The same definition as above.]

H ₂ NCHR ¹ R ² (n1)

[ formula, R ¹ And R is ² The same definition as above.]

Examples of the compound represented by the formula (pt 1) include 3,4,9, 10-perylenetetracarboxylic dianhydride.

Examples of the compound represented by the formula (n 1) include 1-pentylhexylamine (6-aminoundecane) and 1-hexylheptylamine (7-aminotridecane). The compound represented by the formula (n 1) may be used alone or in combination of 2 or more.

The amount of the compound represented by the formula (n 1) to be used is usually 1 to 10 moles, preferably 1 to 8 moles, more preferably 1 to 6 moles, still more preferably 1 to 4 moles, based on 1 mole of the compound represented by the formula (pt 1).

Examples of the solvent include water; nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, 1-octanol, and phenol; ether solvents such as diethyl ether and tetrahydrofuran; ketone solvents such as acetone and methyl isobutyl ketone; ester solvents such as ethyl acetate; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene; 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 to be used is usually 1 to 1000 parts by mass based on 1 part by mass of the compound represented by the formula (pt 1).

The reaction temperature is usually-100℃to 300℃and preferably-90℃to 200℃and more preferably-10℃to 150 ℃.

After the completion of the reaction, the method for removing the compound (I) is not particularly limited, and it can be removed by various known methods. For example, the compound (I) may be removed by distillation of the solvent. After the solvent is distilled off, the obtained residue may be further purified by column chromatography, recrystallization, or the like. After completion of the reaction, the compound (I) may be removed by filtration. After filtration, the obtained residue may be purified by column chromatography, recrystallization, or the like. The chemical structure of the compound (I) obtained can be analyzed by a known analysis method and conditions thereof. Such an analysis method is not particularly limited, and examples thereof include an X-ray crystal structure analysis method, a mass spectrometry (LC), an NMR analysis method, and an elemental analysis method. The analysis of the X-ray crystal structure can be carried out, for example, according to Chemistry of Materials,2012, volume 24, p.4647-4652.

The compound (I-1) can be produced, for example, by reacting 3,4,9, 10-perylene tetracarboxylic dianhydride and 1-hexylheptylamine in a solvent.

The compound (I-2) can be produced, for example, by reacting 3,4,9, 10-perylene tetracarboxylic dianhydride and 1-pentylhexylamine in a solvent.

Fluorescent dye (a) >, fluorescent dye

The fluorescent dye (a) is a dye having fluorescence properties (Photoluminescence) and contains a compound having a structure different from that of the compound represented by the formula (I). The compound having a structure different from that of the compound represented by the formula (I) is preferably a red fluorescent dye.

The red fluorescent dye may be, for example, a compound represented by the following formula (II) (hereinafter, also referred to as compound (II)).

In the formula (II),

R ¹⁵ ～R ¹⁸ Each independently represents a hydrocarbon group having 1 to 40 carbon atoms, a hydrogen atom, a halogen atom or a nitro group which may have a substituent.

As Ar ¹ ～Ar ⁶ Examples of the aryl group include phenyl and naphthyl. As Ar ¹ ～Ar ⁶ Aryl groups represented are preferably phenyl groups.

As Ar ¹ ～Ar ⁶ Examples of the substituent that the aryl group represented may have include substituents selected from the group consisting of a halogen atom, a nitrile group, a nitro group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group, a thiol group, an alkylthio group having 1 to 10 carbon atoms, an allylthio group, a sulfinyl group, an alkylsulfinyl group having 1 to 10 carbon atoms, an arylsulfinyl group, a silyl group, a boron group, an arylamino group, an aralkylamino group, an alkylamino group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, an arylalkenyl group, a heterocyclic group having 3 to 10 carbon atoms and an ethynyl group. Among them, alkyl groups having 1 to 10 carbon atoms and halogen atoms are preferable.

The alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.

Ar ¹ ～Ar ⁶ The aryl group represented may have 1 or 2 or more substituents, or may not have.

As Ar ¹ ～Ar ⁶ Examples thereof include groups represented by the following formulas. * Represents the bonding site.

As Ar ¹ ～Ar ⁶ Preferred substituents are those of the formulae (E-1), (E-4), (E-7), (E-9), (E-17), (E-18) and (E-19). When these groups are used, the fluorescence intensity tends to be high. Ar (Ar) ¹ And Ar is a group ² Preferably the same. Ar (Ar) ³ ～Ar ⁶ The same kind may be used, or different kinds may be used.

Specific examples of the compound (II) include compounds shown in tables 2 to 6 below.

TABLE 2

Ar ¹

Ar ²

Ar ³

Ar ⁴

Ar ⁵

Ar ⁶

R ¹⁵

R ¹⁶

R ¹⁷

R ¹⁸

II-1

E-6

E-1

H

II-2

E-7

E-1

H

II-3

E-10

E-1

H

II-4

E-6

E-4

H

II-5

E-7

E-4

H

II-6

E-10

E-4

H

II-7

E-6

E-9

H

II-8

E-7

E-9

H

II-9

E-10

E-9

H

II-10

E-6

E-17

H

II-11

E-7

E-17

H

II-12

E-10

E-17

H

II-13

E-6

E-18

H

II-14

E-7

E-18

H

II-15

E-10

E-18

H

II-16

E-6

E-19

H

II-17

E-7

E-19

H

II-18

E-10

E-19

H

II-19

E-6

E-1

E-4

H

II-20

E-6

E-1

E-9

H

II-21

E-6

E-1

E-17

H

II-22

E-6

E-1

E-18

H

II-23

E-6

E-1

E-19

H

II-24

E-6

E-1

E-4

H

II-25

E-6

E-1

E-9

H

II-26

E-6

E-1

E-17

H

II-27

E-6

E-1

E-18

H

II-28

E-6

E-1

E-19

H

II-29

E-6

E-1

E-4

H

II-30

E-6

E-1

E-9

H

II-31

E-6

E-1

E-17

H

II-32

E-6

E-1

E-18

H

II-33

E-6

E-1

E-19

H

II-34

E-6

E-4

E-9

H

II-35

E-6

E-4

E-17

H

II-36

E-6

E-4

E-18

H

II-37

E-6

E-4

E-19

H

TABLE 3

Ar ¹

Ar ²

Ar ³

Ar ⁴

Ar ⁵

Ar ⁶

R ¹⁵

R ¹⁶

R ¹⁷

R ¹⁸

II-38

E-6

E-4

E-9

H

II-39

E-6

E-4

E-17

H

II-39

E-6

E-4

E-17

H

II-40

E-6

E-4

E-18

H

II-41

E-6

E-4

E-19

H

II-42

E-6

E-4

E-9

H

II-43

E-6

E-4

E-17

H

II-44

E-6

E-4

E-18

H

II-45

E-6

E-4

E-19

H

II-46

E-6

E-9

E-17

H

II-47

E-6

E-9

E-18

H

II-48

E-6

E-9

E-19

H

II-49

E-6

E-9

E-17

H

II-50

E-6

E-9

E-18

H

II-51

E-6

E-9

E-19

H

II-52

E-6

E-9

E-17

H

II-53

E-6

E-9

E-18

H

II-54

E-6

E-9

E-19

H

II-55

E-6

E-17

E-18

H

II-56

E-6

E-17

E-19

H

II-57

E-6

E-17

E-18

H

II-58

E-6

E-17

E-19

H

II-59

E-6

E-17

E-18

H

II-60

E-6

E-17

E-19

H

II-61

E-6

E-18

E-19

H

II-62

E-6

E-18

E-19

H

II-63

E-6

E-18

E-19

H

II-64

E-7

E-1

E-4

H

II-65

E-7

E-1

E-9

H

II-66

E-7

E-1

E-17

H

II-67

E-7

E-1

E-18

H

II-68

E-7

E-1

E-19

H

II-69

E-7

E-1

E-4

H

II-70

E-7

E-1

E-9

H

II-71

E-7

E-1

E-17

H

II-72

E-7

E-1

E-18

H

II-73

E-7

E-1

E-19

H

TABLE 4

Ar ¹

Ar ²

Ar ³

Ar ⁴

Ar ⁵

Ar ⁶

R ¹⁵

R ¹⁶

R ¹⁷

R ¹⁸

II-74

E-7

E-1

E-4

H

II-75

E-7

E-1

E-9

H

II-76

E-7

E-1

E-17

H

II-77

E-7

E-1

E-18

H

II-78

E-7

E-1

E-19

H

II-79

E-7

E-4

E-9

H

II-80

E-7

E-4

E-17

H

II-81

E-7

E-4

E-18

H

II-82

E-7

E-4

E-19

H

II-83

E-7

E-4

E-9

H

II-84

E-7

E-4

E-17

H

II-85

E-7

E-4

E-18

H

II-86

E-7

E-4

E-19

H

II-87

E-7

E-4

E-9

H

II-88

E-7

E-4

E-17

H

II-89

E-7

E-4

E-18

H

II-90

E-7

E-4

E-19

H

II-91

E-7

E-9

E-17

H

II-92

E-7

E-9

E-18

H

II-93

E-7

E-9

E-19

H

II-94

E-7

E-9

E-17

H

II-95

E-7

E-9

E-18

H

II-96

E-7

E-9

E-19

H

II-97

E-7

E-9

E-17

H

II-98

E-7

E-9

E-18

H

II-99

E-7

E-9

E-19

H

II-100

E-7

E-17

E-18

H

II-101

E-7

E-17

E-19

H

II-102

E-7

E-17

E-18

H

II-103

E-7

E-17

E-19

H

II-104

E-7

E-17

E-18

H

II-105

E-7

E-17

E-19

H

II-106

E-7

E-18

E-19

H

II-107

E-7

E-18

E-19

H

II-108

E-7

E-18

E-19

H

II-109

E-10

E-1

E-4

H

II-110

E-10

E-1

E-9

H

TABLE 5

Ar ¹

Ar ²

Ar ³

Ar ⁴

Ar ⁵

Ar ⁶

R ¹⁵

R ¹⁶

R ¹⁷

R ¹⁸

II-111

E-10

E-1

E-17

H

II-112

E-10

E-1

E-18

H

II-113

E-10

E-1

E-19

H

II-114

E-10

E-1

E-4

H

II-115

E-10

E-1

E-9

H

II-116

E-10

E-1

E-17

H

II-117

E-10

E-1

E-18

H

II-118

E-10

E-1

E-19

H

II-119

E-10

E-1

E-4

H

II-120

E-10

E-1

E-9

H

II-121

E-10

E-1

E-17

H

II-122

E-10

E-1

E-18

H

II-123

E-10

E-1

E-19

H

II-124

E-10

E-4

E-9

H

II-125

E-10

E-4

E-17

H

II-126

E-10

E-4

E-18

H

II-127

E-10

E-4

E-19

H

II-128

E-10

E-4

E-9

H

II-129

E-10

E-4

E-17

H

II-130

E-10

E-4

E-18

H

II-131

E-10

E-4

E-19

H

II-132

E-10

E-4

E-9

H

II-133

E-10

E-4

E-17

H

II-134

E-10

E-4

E-18

H

II-135

E-10

E-4

E-19

H

II-136

E-10

E-9

E-17

H

II-137

E-10

E-9

E-18

H

II-138

E-10

E-9

E-19

H

II-139

E-10

E-9

E-17

H

II-140

E-10

E-9

E-18

H

II-141

E-10

E-9

E-19

H

II-142

E-10

E-9

E-17

H

II-143

E-10

E-9

E-18

H

II-144

E-10

E-9

E-19

H

II-145

E-10

E-17

E-18

H

II-146

E-10

E-17

E-19

H

II-147

E-10

E-17

E-18

H

TABLE 6

Ar ¹

Ar ²

Ar ³

Ar ⁴

Ar ⁵

Ar ⁶

R ¹⁵

R ¹⁶

R ¹⁷

R ¹⁸

II-148

E-10

E-17

E-19

H

II-149

E-10

E-17

E-18

H

II-150

E-10

E-17

E-19

H

II-151

E-10

E-18

E-19

H

II-152

E-10

E-18

E-19

H

II-153

E-10

E-18

E-19

H

The compounds (II-2), (II-4), (II-7), (II-10), (II-13), (II-64) to (II-108) are preferable, the compounds (II-2), (II-4), (II-7), (II-10), (II-91) to (II-99) are more preferable, and the compounds (II-2) and (II-92) are more preferable. These compounds tend to have high solubility in solvents and high fluorescence intensity.

As another preferred embodiment of the compound (II) in the present invention, there may be mentioned compounds represented by the following formulas (II-2) and (II-92), respectively (hereinafter, also referred to as compound (II-2) and compound (II-92)).

The compound (II) can be produced, for example, by reacting a compound represented by the following formula (pt 2), a compound represented by the following formula (AR 1), and a compound represented by the following formula (AR 2) in a solvent.

[ formula, R ⁵ ～R ¹² The same definition as above.]

Ar－NH ₂ (AR1)

Ar－OH (AR2)

[ wherein Ar is as defined above for Ar ¹ ～Ar ⁶ Is the same as defined in the following.]

Examples of the compound represented by the formula (pt 2) include 1,6,7, 12-tetrachloroperylene tetracarboxylic dianhydride and the like.

Examples of the compound represented by the formula (AR 1) include 2, 6-diisopropylaniline, aniline, 3, 5-dimethylaniline, 3, 5-di-t-butylaniline, and the like. The compound represented by the formula (AR 1) may be used alone or in an amount of 2 or more.

Examples of the compound represented by the formula (AR 2) include phenol, 4-fluorophenol, 4-chlorophenol, and 4-bromophenol. The compound represented by the formula (AR 1) may be used alone or in an amount of 2 or more.

The total amount of the compound represented by the formula (AR 1) and the compound represented by the formula (AR 2) to be used is usually 1 to 10 moles, preferably 1 to 8 moles, more preferably 1 to 6 moles, and even more preferably 1 to 4 moles, based on 1 mole of the compound represented by the formula (pt 2).

The solvent may be water; nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, 1-octanol, and phenol; ether solvents such as diethyl ether and tetrahydrofuran; ketone solvents such as acetone and methyl isobutyl ketone; ester solvents such as ethyl acetate; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene; 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, carboxylic acid solvents such as acetic acid, propionic acid, butyric acid, and the like, imidazole, and the like. N-methylpyrrolidone, imidazole and propionic acid are preferred.

The amount of the solvent to be used is usually 1 to 1000 parts by mass based on 1 part by mass of the compound represented by the formula (pt 2).

After the completion of the reaction, the method for removing the compound (II) is not particularly limited, and it can be removed by various known methods. For example, the compound (II) may be removed by distilling off the solvent. After the solvent is distilled off, the obtained residue may be further purified by column chromatography, recrystallization, or the like. After the completion of the reaction, the compound (II) may be removed by filtration. After filtration, the obtained residue may be purified by column chromatography, recrystallization, or the like. The chemical structure of the compound (II) obtained can be analyzed by a known analysis method and conditions thereof. Such an analysis method is not particularly limited, and examples thereof include an X-ray crystal structure analysis method, a mass spectrometry (LC), an NMR analysis method, and an elemental analysis method. The X-ray crystallography can be carried out, for example, according to Chemistry of Materials,2012, volume 24, p.4647-4652.

The compound (II-2) can be produced by reacting 1,6,7, 12-tetrachloroperylene tetracarboxylic dianhydride with 2, 6-diisopropylaniline and phenol in a solvent.

Representative commercial products of the compound (II-2) include Lumogen (registered trademark) F Red 305 and the like.

< colorant (A) >)

The lower limit of the content of the compound (I) in the colorant (a) may be, for example, a value of 0.1 mass% or more relative to the total amount of the colorant (a), and specific examples thereof may be 0.5 mass%, 1 mass%, 5 mass%, 10 mass%, 20 mass%, 50 mass%, 70 mass%, 90 mass%, or the like.

On the other hand, the upper limit of the content of the compound (I) in the colorant (a) may be a value of 99.9 mass% or less, for example, and specific examples thereof may be 99.5 mass%, 99 mass%, 95 mass%, 90 mass%, 80 mass%, 50 mass%, 30 mass%, 10 mass%, or the like, with respect to the total amount of the colorant (a).

For example, when the colorant (a) contains the compound (I) and the compound (II), the content of the compound (I) in the colorant (a) may be, for example, 1 to 99% by mass, preferably 5 to 70% by mass, and more preferably 10 to 50% by mass, relative to the total amount of the colorant (a).

The lower limit value of the content of the fluorescent dye (a) in the colorant (a) may be, for example, a value of 0.1 mass% or more relative to the total amount of the colorant (a), and specific examples thereof may be 0.5 mass%, 1 mass%, 5 mass%, 10 mass%, 20 mass%, 50 mass%, 70 mass%, 90 mass%, or the like.

On the other hand, the upper limit value of the content of the fluorescent dye (a) in the colorant (a) may be, for example, 99.9 mass% or less, and specific examples thereof may be 99.5 mass%, 99 mass%, 95 mass%, 90 mass%, 80 mass%, 50 mass%, 30 mass%, 10 mass% or less, or the like, with respect to the total amount of the colorant (a).

For example, when the colorant (a) contains the compound (I) and the compound (II), the content of the compound (II) in the colorant (a) may be, for example, 1 to 99% by mass, preferably 30 to 95% by mass, and more preferably 50 to 90% by mass, relative to the total amount of the colorant (a).

The content of the compound having a structure different from that of the compound represented by the formula (I) in the fluorescent dye (a) may be, for example, 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 5% by mass or more, particularly preferably 10% by mass or more, still more preferably 20% by mass or more, still more preferably 50% by mass or more, particularly preferably 70% by mass or more, and most preferably 90% by mass or more relative to the total amount of the fluorescent dye (a).

On the other hand, the content of the fluorescent dye (a) in the colorant (a) is usually less than 100% by mass, preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 95% by mass or less, particularly preferably 90% by mass or less, further preferably 80% by mass or less, further preferably 50% by mass or less, particularly preferably 30% by mass or less, and most preferably 10% by mass or less, relative to the total amount of the colorant (a).

When the compound having a structure different from that of the compound represented by the formula (I) is the compound (II), the lower limit value of the content of the compound (II) in the colorant (a) may be, for example, 0.1 mass% or more, and specific examples thereof may be 0.5 mass% or more, 1 mass% or more, 5 mass% or more, 10 mass%, 20 mass%, 50 mass%, 70 mass%, 90 mass% or the like, relative to the total amount of the colorant (a).

On the other hand, the upper limit of the content of the compound (II) in the colorant (a) may be 99.9 mass% or less, for example, and specific examples thereof may be 99.5 mass%, 99 mass%, 95 mass%, 90 mass%, 80 mass%, 50 mass%, 30 mass%, 10 mass%, or the like, relative to the total amount of the colorant (a).

By including the compound (I) and the fluorescent dye (a) in the colorant (a), the fluorescent intensity of the fluorescent dye (a) tends to be improved.

The mass ratio of the compound (I) to the fluorescent dye (a) in the colorant (A) may be, for example, 1:99 to 99:1, preferably 20:80 to 80:20, and more preferably 30:70 to 70:30. When the mass ratio of the compound (I) to the fluorescent dye (a) in the colorant (a) is in the above range, heat resistance and fluorescence intensity tend to be easily improved.

The mass ratio of the compound (I) to the compound (II) in the colorant (A) may be, for example, 1:99 to 99:1, preferably 20:80 to 80:20, and more preferably 30:70 to 70:30.

The content of the colorant (a) in the coloring composition may be, for example, 0.1 to 99.9% by mass, preferably 0.5 to 99% by mass, more preferably 1 to 95% by mass, still more preferably 3 to 90% by mass, particularly preferably 10 to 80% by mass, still more preferably 10 to 60% by mass, and still more preferably 10 to 35% by mass, relative to the total amount of solid components in the coloring composition.

In the present specification, the "total amount of solid components in the coloring composition" refers to the total amount of components other than all solvent components in the coloring composition. The total amount of the solid components and the content of each component relative thereto can be measured by a known analytical method such as liquid chromatography or gas chromatography.

< colorant (A1) >)

The colorant (A1) may be a dye or a pigment. As the dye, a known dye can be used, and examples thereof include a known dye described in color index (The Society of Dyers and Colourists publication) and dyeing guide (color dyeing company). Further, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitrodyes, phthalocyanine dyes, perylene dyes, and the like can be exemplified. These dyes may be used singly or in combination of 2 or more.

Specifically, the following color index (c.i.) numbered dyes are exemplified.

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, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;

C.i. solvents 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. solvents green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc.,

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, 401, 412, 417, 418, 422, 426;

C.i. acid oranges 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, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 249, 256, 259, 267, 269, 280, 290, 296, 278, 315, 340.

C.i. acid green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109, etc.,

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 oranges 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, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274.

C.i. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82, etc.,

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

c.i. disperse violet 26, 27;

c.i. disperse blue 1, 14, 56, 60, etc.,

c.i. basic red 1, 10;

c.i. basic blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89;

c.i. basic violet 2;

c.i. basic red 9;

c.i. basic dyes such as c.i. basic green 1,

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

c.i. active orange 16;

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

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

c.i. media red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;

c.i. medium oranges 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

c.i. vehicle violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58;

C.i. medium blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;

c.i. mediator dyes of c.i. mediator green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53, etc.,

C.I. vat dyes such as C.I. vat green 1, etc.

Further, lumogen (registered trademark) F yellow 083 (manufactured by BASF), lumogen (registered trademark) F yellow 170 (manufactured by BASF), and Lumogen (registered trademark) F orange 240 (manufactured by BASF) can be cited.

As the pigment, a known pigment can be used, and examples thereof include pigments classified as pigments (pigment) in the color index (The Society of Dyers and Colourists publication). These may be used alone or in combination of 2 or more.

Specifically, examples thereof include yellow pigments such as c.i. pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, 231;

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

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, 265, 266, 268, 269, 273;

c.i. pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, etc. blue pigments;

violet pigments such as c.i. pigment violet 1, 19, 23, 29, 32, 36, 38;

green pigments such as c.i. pigment green 7, 36, 58, 59, 62, 63;

brown pigments such as pigment brown 23, 25;

black pigments such as c.i. pigment black 1, 7, 31, 32.

The colorant (A1) may be subjected to a rosin treatment, a surface treatment using a derivative having an acidic group or a basic group introduced therein, a grafting treatment to the surface of the colorant (A1) based on a polymer compound or the like, a micronization treatment by sulfuric acid micronization or the like, a washing treatment by an organic solvent, water or the like for removing impurities, a removal treatment by an ion exchange method or the like for ionic impurities, or the like, as required. The particle diameter of the colorant (A1) is preferably substantially uniform.

When the colorant (a) further contains the colorant (A1), the lower limit of the total content of the compound (I) and the compound (II) in the colorant (a) is usually 1% by mass or more, preferably 2% by mass or more, more preferably 10% by mass or more, still more preferably 25% by mass or more, and particularly preferably 50% by mass or more, relative to the total amount of the colorant (a). On the other hand, the upper limit of the total content of the compound (I) and the compound (II) in the colorant (a) is usually less than 100 mass% relative to the total amount of the colorant (a).

When the colorant (a) further contains the colorant (A1), the content of the colorant (a) in the coloring composition is usually 0.1 to 99% by mass, for example, may be 0.1 to 90% by mass, preferably 0.5 to 80% by mass, more preferably 0.7 to 70% by mass, and particularly preferably 1 to 60% by mass, relative to the total amount of solid components in the coloring composition.

When the coloring composition contains the solvent (E), a coloring composition may be prepared by preparing a coloring agent-containing solution containing the coloring agent (a) and the solvent (E) in advance and then using the coloring agent-containing solution. When the colorant (a) is insoluble in the solvent (E), a solution containing the colorant can be prepared by dispersing the colorant (a) in the solvent (E) and mixing. The colorant-containing solution may contain a part or all of the solvent (E) contained in the coloring composition.

The content of the solid component in the colorant-containing solution is preferably 0.01 to 99.99% by mass, more preferably 0.1 to 99.9% by mass, still more preferably 0.1 to 99% by mass, particularly preferably 1 to 90% by mass, still more preferably 1 to 60% by mass, still more preferably 3 to 50% by mass, particularly preferably 3 to 30% by mass, and most preferably 5 to 30% by mass, relative to the total amount of the colorant-containing solution.

The content of the colorant (a) in the colorant-containing solution is usually less than 100% by mass, preferably 0.0001% by mass to 99.9999% by mass, more preferably 0.01% by mass to 99% by mass, still more preferably 0.1% by mass to 99% by mass, particularly preferably 1% by mass to 99% by mass, and still more preferably 2% by mass to 99% by mass, based on the total amount of solid components in the colorant-containing solution.

In the present specification, the "total amount of solid components in the colorant-containing solution" refers to the total amount of components other than the solvent (E) from the colorant-containing solution. The total amount of the solid components and the content of each component relative to the total amount can be measured by a known analytical method such as liquid chromatography or gas chromatography.

The colorant (A1) may be dispersed by a dispersing treatment with a dispersant, whereby the colorant (A1) is uniformly dispersed in a solution containing the colorant (A1). The colorant (A1) may be dispersed alone or in combination of two or more.

The dispersant may be any of cationic, anionic, nonionic, and amphoteric surfactants. Specifically, examples thereof include surfactants such as polyester-based, polyamine-based and acrylic-based surfactants. These dispersants may be used singly or in combination of two or more. Examples of the dispersant include KP (manufactured by Xinyue chemical industry Co., ltd.), FLOWLEN (manufactured by Kyowa chemical Co., ltd.), solsperse (registered trademark) (manufactured by Zeneca Co., ltd.), EFKA (registered trademark) (manufactured by BASF), AJISPER (registered trademark) (manufactured by Weisu Fine chemical Co., ltd.), disperbyk (registered trademark) (manufactured by BYK-Chemie Co., ltd.), and BYK (registered trademark) (manufactured by BYK-Chemie Co., ltd.).

When a dispersant is used for preparing the above-mentioned colorant-containing solution, the amount of the dispersant (solid content) to be used is usually 10000 parts by mass or less, preferably 5000 parts by mass or less, more preferably 1000 parts by mass or less, still more preferably 500 parts by mass or less, particularly preferably 300 parts by mass or less, still more preferably 100 parts by mass or less, still more preferably 5 parts by mass to 100 parts by mass, and particularly preferably 5 parts by mass to 50 parts by mass, based on 100 parts by mass of the colorant (a). When the amount of the dispersant is within the above range, a colorant-containing solution in a more uniform dispersion state tends to be obtained.

< resin (B) >)

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

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

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

Examples of the monomer (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, and p-vinylbenzoic acid;

unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5, 6-tetrahydrophthalic acid, 1,2,3, 6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid and 1, 4-cyclohexene dicarboxylic acid;

2-unsaturated compounds containing a carboxyl group such as methyl 5-norbornene-2, 3-dicarboxylate, 5-carboxybicyclo [2.2.1] hept-2-ene, 5, 6-dicarboxyibicyclo [2.2.1] hept-2-ene, 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 excluding fumaric acid and methyl fumaric acid;

unsaturated mono- [ (meth) acryloyloxyalkyl ] esters of polycarboxylic acids having 2 or more members such as succinic acid mono- [ 2- (meth) acryloyloxyethyl ester ] and phthalic acid mono- [ 2- (meth) acryloyloxyethyl ester ];

unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as α - (hydroxymethyl) acrylic acid.

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

The monomer (b) is a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least 1 selected from the group consisting of an ethylene oxide ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. The monomer (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

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

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

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

Specific examples of the monomer (b 1-1) include glycidyl (meth) acrylate, β -methyl glycidyl (meth) acrylate, β -ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, vinylbenzyl glycidyl ether, α -methyl vinylbenzyl glycidyl ether, 2, 3-bis (glycidoxymethyl) styrene, 2, 4-bis (glycidoxymethyl) styrene, 2, 5-bis (glycidoxymethyl) styrene, 2, 6-bis (glycidoxymethyl) styrene, 2,3, 4-tris (glycidoxymethyl) styrene, 2,3, 5-tris (glycidoxymethyl) styrene, 2,3, 6-tris (glycidoxymethyl) styrene, 3,4, 5-tris (glycidoxymethyl) styrene and 2,4, 6-tris (glycidoxymethyl) styrene.

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

[ formula (BI) and formula (BII), R ^a And R is ^b Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X ^a And X ^b Each independently represents a single bond, -R ^c －、*－R ^c －O－、*－R ^c -S-or-R ^c －NH－。

R ^c Represents an alkanediyl group having 1 to 6 carbon atoms.

* Represents the bonding site to O. ]

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

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

As R ^a And R is ^b The hydrogen atom, methyl group, hydroxymethyl group, 1-hydroxyethyl group and 2-hydroxyethyl group are preferable, and the hydrogen atom and methyl group are more preferable.

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

As X ^a And X ^b A single bond, methylene, ethylene, or-CH may be preferably mentioned ₂ -O-and-CH ₂ CH ₂ O-, more preferably a single bond, -CH ₂ CH ₂ -O- (x) represents a bonding site to O.

The compound represented by the formula (BI) may be a compound represented by any one of the formulas (BI-1) to (BI-15), or the like. Among them, compounds represented by the formulas (BI-1), (BI-3), formula (BI-5), formula (BI-7), formula (BI-9) and formulas (BI-11) to (BI-15) are preferable, and compounds represented by the formulas (BI-1), formula (BI-7), formula (BI-9) and formula (BI-15) are more preferable.

The compound represented by the formula (BII) may be a compound represented by any one of the formulas (BII-1) to (BII-15), and among them, the compounds represented by the formulas (BII-1), (BII-3), the formulas (BII-5), the formulas (BII-7), the formulas (BII-9) and the formulas (BII-11) to (BII-15) may be preferable, and the compounds represented by the formulas (BII-1), the formulas (BII-7), the formulas (BII-9) and the formulas (BII-15) may be more preferable.

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

As the monomer (b 2), monomers having an oxetanyl group and a (meth) acryloyloxy group are more preferable.

Examples of the monomer (b 2) include 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, and 3-ethyl-3-acryloyloxyethyl oxetane.

As the monomer (b 3), a monomer having a tetrahydrofuranyl group and a (meth) acryloyloxy group is more preferable.

Examples of the monomer (b 3) include tetrahydrofurfuryl acrylate (for example, viscoat V#150, manufactured by Osaka organic chemical industry Co., ltd.), and tetrahydrofurfuryl methacrylate.

The monomer (b) is preferably the monomer (b 1) in order to improve reliability such as heat resistance and chemical resistance of the color filter obtained. Further, the monomer (b 1-2) is more preferable in view of excellent storage stability of the coloring composition.

Examples of the monomer (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo [5.2.1.0 ] acrylate ^2,6 ]Decane-8-yl ester, tricyclo [5.2.1.0 (meth) acrylic acid ^2,6 ]Decane-9-yl ester, tricyclo [5.2.1.0 (meth) acrylic acid ^2,6 ]Decen-8-yl ester, tricyclo (meth) acrylate [5.2.1.0 ^2,6 ](meth) acrylic esters such as decen-9-yl ester, dicyclopentyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthalene (meth) acrylate, and benzyl (meth) acrylate;

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

dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

Bicyclo [2.2.1] hept-2-ene, 5-methyl-bicyclo [2.2.1] hept-2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-hydroxy-bicyclo [2.2.1] hept-2-ene, 5- (2 '-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxy-bicyclo [2.2.1] hept-2-ene, 5-ethoxy-bicyclo [2.2.1] hept-2-ene, 5, 6-dihydroxy-bicyclo [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-dimethoxy-bicyclo [ 2.1] hept-2-ene, 5, 6-diethoxy-bicyclo [ 2.1] hept-2-ene, 5-diethoxy-2.1 ] bicyclo [ 2.1] hept-2-ene, 5-ethoxy-2.1 ] bicyclohexa-2-ene, 5-hydroxy-2-carbonyl-2.1-ene, 5-dihydroxy-bicyclo [2.2.1] hept-ene, 5-hydroxy-2.1 ] bicyclooxy-carbonyl-2-ene, 5-hydroxy-bicyclo [ 2.1.1 ] bicyclooxy-2.1 ] hept-ene;

Dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N- (9-acridinyl) maleimide;

vinyl-containing aromatic compounds such as styrene, α -methylstyrene, vinyltoluene, and p-methoxystyrene; vinyl-containing nitriles such as (meth) acrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; vinyl-containing amides such as (meth) acrylamide; esters such as vinyl acetate; dienes such as 1, 3-butadiene, isoprene and 2, 3-dimethyl-1, 3-butadiene.

Among them, from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyl toluene, tricyclo (meth) acrylate [5.2.1.0 ] are preferable ^2,6 ]Decane-8-yl ester, tricyclo [5.2.1.0 (meth) acrylic acid ² _, ⁶ ]Decane-9-yl ester, tricyclo [5.2.1.0 (meth) acrylic acid ^2,6 ]Decen-8-yl ester, tricyclo (meth) acrylate [5.2.1.0 ^2,6 ]Decen-9-yl ester, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1 ]Hept-2-ene and benzyl (meth) acrylate, and the like.

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 can be obtained by adding a monomer having a group reactive with the groups of the monomers (a) and (b) and an ethylenically unsaturated bond to a polymer having a structural unit derived from the monomers (a) and (b).

Examples of such a structural unit include a structural unit obtained by adding a glycidyl (meth) acrylate to a (meth) acrylic acid unit, a structural unit obtained by adding a 2-hydroxyethyl (meth) acrylate to a maleic anhydride unit, and a structural unit obtained by adding a glycidyl (meth) acrylate to a (meth) acrylic acid unit. When these structural units have a hydroxyl group, a structural unit to which a carboxylic acid anhydride is further added may be mentioned as a structural unit having an ethylenically unsaturated bond.

The polymer having the 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, solvent, and the like are not particularly limited, and those generally used in the art can be used. For example, as the polymerization initiator, azo compounds (2, 2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile) and the like), organic peroxides (benzoyl peroxide and the like) may be cited, and as the solvent, any solvent may be used as long as it dissolves the respective monomers.

The resulting polymer may be used as it is, concentrated or diluted, or may be extracted as a solid (powder) by a method such as reprecipitation.

If necessary, a catalyst for the reaction of carboxylic acid or carboxylic anhydride with cyclic ether (for example, tris (dimethylaminomethyl) phenol and the like) and a polymerization inhibitor (for example, hydroquinone and the like) and the like can also be used.

Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5, 6-dicarboxyibicyclo [2.2.1] hept-2-ene anhydride.

Specific examples of the resin (B) include 3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid copolymer and 3, 4-epoxytricyclo (meth) acrylate [5.2.1.0 ] ^2,6 ]Decyl ester/(meth) acrylic acidCopolymers, glycidyl (meth) acrylate/(meth) acrylic acid benzyl/(meth) acrylic acid copolymers, glycidyl (meth) acrylate/styrene/(meth) acrylic acid copolymers, 3, 4-epoxytricyclo (meth) acrylic acid [5.2.1.0 ^2,6 ]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, 3, 4-epoxytricyclo (meth) acrylic acid [5.2.1.0 ^2,6 ]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, 3, 4-epoxytricyclo (meth) acrylic acid 5.2.1.0 ^2,6 ]Decyl ester/(meth) acrylic acid/vinyltoluene copolymer, 3, 4-epoxytricyclo (meth) acrylic acid [5.2.1.0 ^2,6 ]Decyl ester/(meth) acrylic acid 2-ethylhexyl ester copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] of (meth) acrylic acid ^2,6 ]Decyl ester/tricyclo (meth) acrylate [5.2.1.0 ^2,6 ]Decenyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, 3-methyl-3- (meth) acryloyloxymethyl oxetane/(meth) acrylic acid/styrene copolymer, benzyl (meth) acrylate/(meth) acrylic acid copolymer, styrene/(meth) acrylic acid copolymer, resins described in each of Japanese patent application laid-open No. 9-106071, japanese patent application laid-open No. 2004-29518 and Japanese patent application laid-open No. 2004-361455, and the like.

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 combined with 2 or more, in which case the resin (B) preferably contains at least one compound selected from 3, 4-epoxytricyclo [5.2.1.0 ] of (meth) acrylic acid ^2,6 ]Decyl ester/(meth) acrylic acid copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] of (meth) acrylic acid ^2,6 ]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, 3, 4-epoxytricyclo (meth) acrylic acid 5.2.1.0 ^2,6 ]Decyl ester/(meth) acrylic acid/vinyltoluene copolymer, 3, 4-epoxytricyclo (meth) acrylic acid [5.2.1.0 ^2,6 ]More than 1 kind of decyl ester/(methyl) acrylic acid 2-ethylhexyl ester copolymer.

The polystyrene-equivalent weight average molecular weight (Mw) of the resin (B) is preferably 1000 to 100000, more preferably 1000 to 50000, further preferably 1000 to 30000, particularly preferably 3000 to 30000.

The molecular weight distribution [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the resin (B) is preferably 1 to 6, more preferably 1.001 to 4, still more preferably 1.01 to 4.

The acid value (solid content conversion value) of the resin (B) is preferably 10mg-KOH/g to 300mg-KOH/g, more preferably 20mg-KOH/g to 250mg-KOH/g, still more preferably 20mg-KOH/g to 200mg-KOH/g, particularly preferably 20mg-KOH/g to 170mg-KOH/g, still more preferably 30mg-KOH/g to 170mg-KOH/g, particularly preferably 60mg-KOH/g to 150mg-KOH/g, and most preferably 65mg-KOH/g to 135mg-KOH/g. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1g of the resin (B), and can be obtained 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 to 99.9% by mass, preferably 0.5 to 99% by mass, more preferably 1 to 95% by mass, still more preferably 5 to 90% by mass, and particularly preferably 20 to 90% by mass, based on the total amount of solid components in the coloring composition.

When the coloring composition of the present invention is prepared by using the colorant-containing solution after the colorant-containing solution is prepared in advance, the colorant-containing solution may contain a part or all, preferably a part of the resin (B) described later contained in the coloring composition in advance. By previously containing the resin (B), the dispersion stability of the colorant-containing solution can be further improved.

The content of the resin (B) in the colorant-containing solution may be 10000 parts by mass or less, preferably 5000 parts by mass or less, more preferably 1000 parts by mass or less, further preferably 1 to 500 parts by mass, particularly preferably 5 to 200 parts by mass, further preferably 10 to 100 parts by mass, per 100 parts by mass of the colorant (a).

Embodiment 1 >

The coloring composition of embodiment 1 is a coloring composition containing a colorant (A) and a resin (B), wherein the colorant (A) contains a compound represented by the following formula (I-1) and a compound represented by the following formula (II-2).

Embodiment 2 >

The coloring composition of embodiment 2 is a coloring composition containing a colorant (A) and a resin (B), wherein the colorant (A) contains a compound represented by the following formula (I-2) and a compound represented by the following formula (II-2).

(2) Colored curable resin composition

The colored curable resin composition contains a compound (I), a fluorescent dye (a) (hereinafter, these are also collectively referred to as a colorant (a)), a resin (B), a polymerizable compound (hereinafter, referred to as a polymerizable compound (C)), and a polymerization initiator (hereinafter, referred to as a polymerization initiator (D)).

The colored curable resin composition may further contain 1 kind selected from a leveling agent (hereinafter, sometimes referred to as leveling agent (F)), an antioxidant (hereinafter, sometimes referred to as antioxidant (G)), and a solvent (E).

The content of the solid component in the colored composition contained in the colored curable resin composition is not particularly limited, since it is appropriately adjusted according to the chromaticity, brightness, film thickness, etc. required when the colored curable resin composition is cured, and may be, for example, 1 to 99% by mass, preferably 1 to 90% by mass, more preferably 2 to 80% by mass, still more preferably 3 to 70% by mass, particularly preferably 4 to 60% by mass, still more preferably 5 to 50% by mass, particularly preferably 6 to 45% by mass, and most preferably 7 to 40% by mass, based on the total amount of the solid component in the colored curable resin composition.

The content of each of the colorants (a) in the photocurable resin composition is not particularly limited, since it is appropriately adjusted according to the chromaticity, brightness, film thickness, etc. required when the photocurable resin composition is cured, and may be, for example, 0.1 to 99% by mass, preferably 1 to 90% by mass, more preferably 2 to 80% by mass, still more preferably 3 to 70% by mass, and particularly preferably 4 to 20% by mass, based on the total amount of solid components in the photocurable resin composition.

In the present specification, the "total amount of solid components in the color curable resin composition" refers to the total amount of components other than the solvent (E) in the color curable resin composition. The total amount of the solid components and the content of each component relative to the total amount can be measured by a known analytical method such as liquid chromatography or gas chromatography. The content of the solid component in the curable resin composition may be, for example, 0.01 mass% or more and less than 100 mass%, preferably 0.1 mass% to 99.9 mass%, more preferably 0.1 mass% to 99 mass%, still more preferably 1 mass% to 90 mass%, particularly preferably 1 mass% to 60 mass%, still more preferably 3 mass% to 50 mass%, still more preferably 3 mass% to 30 mass%, and particularly preferably 5 mass% to 30 mass%, relative to the total amount of the curable resin composition.

The colored pattern and colored coating film formed from the colored curable resin composition of the present invention have not only excellent heat resistance but also a tendency to have a high fluorescence intensity at a wavelength of 610nm, and preferably have a higher fluorescence intensity at a wavelength of 610nm than those formed from the colored curable resin composition containing the fluorescent dye (a) alone. The fluorescence intensity can be measured, for example, using a fluorescence spectrophotometer (FluoMAX-3; manufactured by horiba, inc.).

< polymerizable Compound (C) >)

The polymerizable compound (C) is a compound polymerizable by a living radical and/or an acid generated by the polymerization initiator (D), and is, for example, a compound having a polymerizable ethylenically unsaturated bond, etc., preferably a (meth) acrylate compound.

Examples of the polymerizable compound having 1 ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the like, and the above-mentioned monomer (a), monomer (b), and monomer (c).

Examples of the polymerizable compound having 2 ethylenically unsaturated bonds include 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol a, and 3-methylpentanediol di (meth) acrylate.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

The weight average molecular weight of the polymerizable compound (C) is preferably 50 to 4000, more preferably 50 to 3500, further preferably 50 to 3000, particularly preferably 150 to 2900, and particularly preferably 250 to 1500.

The content of the polymerizable compound (C) in the colored curable resin composition may be, for example, 1 to 99% by mass, preferably 2 to 90% by mass, more preferably 5 to 80% by mass, still more preferably 10 to 70% by mass, and particularly preferably 20 to 70% by mass, based on the total amount of solid components.

Polymerization initiator (D) >)

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating a living radical, an acid, or the like under 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, alkyl phenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.

As the O-acyl oxime compound, for example, examples thereof include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-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-dioxacyclopentylmethoxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-one-2-imine, and the like. As the O-acyl oxime compound, commercially available products such as Irgacure OXE01, OXE02 (both of them are manufactured by BASF) and N-1919 (manufactured by ADEKA) can be used. Among them, as the O-acyloxime compound, at least 1 selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine is preferable, and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine is more preferable.

Examples of the alkylbenzene ketone compound include 2-methyl-2-morpholino-1- (4-methylsulfanyl phenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, and 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] butan-1-one. As the alkylbenzene ketone compound, commercially available products such as Irgacure 369, 907 and 379 (all of which are manufactured by BASF) can be used.

Examples of the alkylbenzene ketone compound include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexylphenyl ketone, an oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone and benzildimethyl ketal.

Examples of the bisimidazole compound include 2,2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbisimidazole and 2,2' -bis (2, 3-dichlorophenyl) -4,4', 5' -tetraphenylbisimidazole (for example, reference is made to Japanese patent application laid-open No. 6-75372, japanese patent application laid-open No. 6-75373, etc.), 2' -bis (2-chlorophenyl) -4,4', 5' -tetra (alkoxyphenyl) bisimidazole, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (dialkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4,4', 5' -tetrakis (trialkoxyphenyl) biimidazole (for example, refer to Japanese patent publication No. 48-38403, japanese patent application laid-open No. 62-174204, etc.), biimidazole compounds in which phenyl groups at the 4,4', 5' -positions are substituted with carboalkoxy groups (for example, refer to Japanese patent application laid-open No. 7-10913, etc.), and the like.

Examples of the triazine compound include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (5-methylfuran-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (furan-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3, 5-triazine, and 2, 4-bis (trichloromethyl) -6- [ 2- (3, 4-dimethoxyphenyl) vinyl ] -1,3, 5-triazine.

Examples of the acylphosphine oxide compound include 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide and the like. Commercial products such as Irgacure 819 (registered trademark) manufactured by BASF can be used.

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

These are preferably used in combination with a polymerization initiator (D1) (particularly an amine) to be described later.

The polymerization initiator (D) is preferably a polymerization initiator containing at least 1 selected from the group consisting of an alkylbenzene ketone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound and a biimidazole compound, and more preferably a polymerization initiator containing an O-acyloxime compound.

The content of the polymerization initiator (D) may be, for example, 0.01 to 40% by mass, and preferably 1 to 35% by mass, based on the total amount of all the resins (B) and polymerizable compounds (C) contained in the colored curable resin composition.

Polymerization initiation aid (D1) >, polymerization initiation aid

The polymerization initiator aid (D1) is a compound or sensitizer for promoting the polymerization of a polymerizable compound that initiates polymerization by a polymerization initiator. When the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiator aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds, and the like.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N-dimethyl-p-toluidine, 4' -bis (dimethylamino) benzophenone (known as Michaelis ' ketone), 4' -bis (diethylamino) benzophenone, and 4,4' -bis (ethylmethylamino) benzophenone, and 4,4' -bis (diethylamino) benzophenone may be preferably used. As the amine compound, commercially available products such as EAB-F (manufactured by Baogu chemical Co., ltd.) can be used.

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

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

Examples of the carboxylic acid compound include phenylthioalkyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylthioalkyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylthioalkyl acetic acid, dimethoxyphenylthioalkyl acetic acid, chlorophenyl thioalkyl acetic acid, dichlorophenylthioalkyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthyloxyacetic acid.

When these polymerization initiator additives (D1) are used, the content thereof may be, for example, 0.01 to 40% by mass, and preferably 0.1 to 30% by mass, relative to the total amount of the resin (B) and the polymerizable compound (C).

Solvent (E) >, solvent (E)

For the solvent (E), for example, examples thereof include an ester solvent (a solvent containing-COO-and not containing-O-in the molecule) an ether solvent (a solvent containing-O-and not-COO-in the molecule), an ether ester solvent (a solvent containing-COO-and-O-in the molecule), a solvent containing-COO-in the molecule, and a solvent containing-COO-in the molecule an ether solvent (a solvent containing-O-and not-COO-in the molecule) ether ester solvents (solvents containing-COO-and-O-in the molecule).

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, 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 gamma-butyrolactone.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, and 1, 4-di-n Alkyl, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methylanisole and the like.

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

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

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, and mesitylene.

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

These solvents may be used in combination of 2 or more.

The content of the solvent (E) is usually 99.99 mass% or less, preferably 0.1 mass% to 99.9 mass%, more preferably 1 mass% to 99.9 mass%, still more preferably 10 mass% to 99 mass%, particularly preferably 40 mass% to 99 mass%, still more preferably 50 mass% to 97 mass%, particularly preferably 70 mass% to 97 mass%, and most preferably 70 mass% to 90 mass% relative to the total amount of the colored curable resin composition.

The colored curable resin composition of the present invention can be prepared by dispersing all or a part of the compound (I) and the fluorescent dye (a) in all or a part of the solvent (E) to prepare a colorant-containing solution, and then using the colorant-containing solution.

The content of the solid component in the colorant-containing solution may be, for example, 0.01 to 99.99% by mass, preferably 0.1 to 99.9% by mass, more preferably 0.1 to 99% by mass, still more preferably 1 to 90% by mass, still more preferably 1 to 60% by mass, still more preferably 3 to 50% by mass, and particularly preferably 3 to 30% by mass, relative to the total amount of the colorant-containing solution.

The total content of the compound (I) and the fluorescent dye (a) in the colorant-containing solution may be, for example, 0.0001% by mass or more, preferably 0.01% by mass or more, more preferably 1% by mass or more, still more preferably 5% by mass or more, still more preferably 10% by mass or more, and still more preferably 15% by mass or more, based on the total amount of solid components in the colorant-containing solution. On the other hand, the upper limit of the total content of the compound (I) and the compound (II) in the colorant-containing solution is usually less than 100 mass%, for example, 99 mass% or less, based on the total amount of the solid components in the colorant-containing solution.

When the colorant-containing solution is prepared by dispersing all or a part of the compound (I) and the fluorescent dye (a) in all or a part of the solvent (E), the dispersion stability of the colorant-containing solution can be further improved by previously containing all or a part of the resin (B). The content of the resin (B) in the colorant-containing solution may be 10000 parts by mass or less, preferably 5000 parts by mass or less, more preferably 1000 parts by mass or less, further preferably 1 to 500 parts by mass, particularly preferably 5 to 200 parts by mass, further preferably 10 to 100 parts by mass, based on 100 parts by mass of the total of the compound (I) and the fluorescent dye (a).

The compound (I) and the fluorescent dye (a) may be subjected to a rosin treatment, a surface treatment using a derivative having an acidic group or a basic group introduced therein, a grafting treatment of the surface of the compound (I) and the fluorescent dye (a) with a polymer compound or the like, a micronization treatment by sulfuric acid micronization or the like, a washing treatment by an organic solvent, water or the like for removing impurities, a removal treatment by an ion exchange method or the like for ionic impurities, or the like, as required. The particle diameters of the compound (I) and the fluorescent dye (a) are preferably substantially uniform.

The compound (I) and the fluorescent dye (a) can be brought into a state of being uniformly dispersed in a solution containing a colorant by performing dispersion treatment with a dispersant. The compound (I) and the fluorescent dye (a) may be dispersed separately or in combination. By including the compound (I), the fluorescent dye (a), and the dispersant in the colorant (a), dispersibility of the compound (I) is improved, and heat resistance tends to be easily improved.

When the dispersant is used, the amount of the dispersant (solid content) to be used is 10000 parts by mass or less, preferably 5000 parts by mass or less, more preferably 1000 parts by mass or less, still more preferably 500 parts by mass or less, particularly preferably 300 parts by mass or less, still more preferably 100 parts by mass or less, still more preferably 5 parts by mass to 100 parts by mass, particularly preferably 5 parts by mass to 50 parts by mass, based on 100 parts by mass of the total of the compound (I) and the fluorescent dye (a). When the amount of the dispersant is within the above range, a colorant-containing solution in a more uniform dispersion state tends to be obtained.

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

< leveling agent (F) >)

Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms. They may have a polymerizable group in a side chain.

Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, toray Silicone DC PA, toray Silicone SH PA, toray Silicone DC11PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH8400 (trade name: dow Corning Toray, manufactured by Kyowa Co., ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Xinyue chemical industries, inc.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by MOMENTIVE PERFORMANCE MATERIALS JAPAN contract Co., ltd.) and the like are exemplified.

The fluorine-based surfactant may be a surfactant having a fluorocarbon chain in the molecule. Specifically, examples thereof include FLUORAD FC430, FLUORAD FC431 (manufactured by Sumitomo 3M (Inc.), MEGAFAC F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC (Inc.), F-top EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi (Inc.), surflon S381, surflon S382, surflon SC101, surflon SC105 (manufactured by Asahi Nitro) and E5844 (manufactured by Mitsubishi gold fine chemical corporation).

Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, there are exemplified MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, MEGAFAC F443 (DIC corporation), and the like.

When the leveling agent (F) is contained, the content thereof is usually 0.0005 mass% to 5 mass%, preferably 0.001 mass% to 1 mass%, more preferably 0.001 mass% to 0.5 mass%, and even more preferably 0.005 mass% to 0.1 mass% relative to the total amount of the colored curable resin composition. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

Antioxidant (G) >

From the viewpoint of improving the heat resistance of the colorant, the antioxidant (G) is preferably used alone or in combination of 2 or more. The antioxidant is not particularly limited as long as it is an antioxidant generally used in industry, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like can be used.

Examples of the phenolic antioxidants include Irganox 1010 (Irganox 1010: pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], manufactured by BASF), irganox 1076 (Irganox 1076: octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, irganox 1330 (Irganox 1330:3,3',3", 5',5" -hexatert-butyl-a, a ', a "- (mesitylene-2, 4, 6-triyl) tri-p-cresol, manufactured by BASF), irganox 3114 (Irganox 3114:1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1 h,3h,5 h) -trione, manufactured by BASF), irganox 3790 (Irganox 3790:1,3, 5-tris ((4-tert-butyl-3-hydroxy-2, 6-xylyl) methyl) -1,3, 5-triazine-2, 4,6 (1 h,3h,5 h) -trione, manufactured by BASF), irganox 1035 (Irganox 1035: thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], BASF), irganox1135 (Irganox 1135: phenylpropane acid, 3, 5-bis (1, 1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, BASF), irganox 1520L (Irganox 1520L:4, 6-bis (octylthiomethyl) -o-cresol, BASF), irganox 3125 (Irganox 3125, BASF), irganox 565 (Irganox 565:2, 4-bis (n-octylthio) -6- (4-hydroxy 3',5' -di-tert-butylphenylamino) -1,3, 5-triazine, BASF), ADK STAB AO-80 (ADK STAB AO-80:3, 9-bis (2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1, 1-dimethylethyl) -2,4,8, 10-tetraoxaspiro (5, 5) undecane (manufactured by ADEKA), sumizer BHT (manufactured by Sumizer BHT, manufactured by Sumitomo chemical Co., ltd.), sumizer GA-80 (manufactured by Sumizer GA-80, manufactured by Sumitomo chemical Co., ltd.), sumizer GS (manufactured by Sumizer GS, manufactured by Sumizer chemical Co., ltd.), cyanox 1790 (manufactured by Cyanox 1790, manufactured by Sitech), vitamin E (manufactured by Eisai), and the like.

Examples of the phosphorus antioxidant include Irgafos 168 (Irgafos 168: tris (2, 4-di-t-butylphenyl) phosphite, irgafos 12 (manufactured by BASF), irgafos 12: tris [2- [ [2,4,8, 10-tetra-t-butyldibenzo [ d, f ] [1,3,2] dioxa-phospha-6-yl ] oxy ] ethyl ] amine, manufactured by BASF), irgafos 38 (manufactured by Irgafos 38: bis (2, 4-bis (1, 1-dimethylethyl) -6-methylphenyl) ethyl phosphite, manufactured by BASF), ADK STAB 329K ((manufactured by ADEKA), ADK STAB PEP36 ((manufactured by ADEKA), ADK STAB-8 ((manufactured by ADEKA), sandstab P-EPQ (manufactured by Clariant Co., ltd.), weston618 (manufactured by Weston618, GE Co., ltd.), weston G619G (manufactured by GE Co., ltd.), ultranox (manufactured by Ultranox, sulzem.) and Suftp-6-methylphenyl) 6- (4-t-butylphospha 6-4-hydroxy-4-propyl) phenyl group (manufactured by Surbridge 2, 6-t-butylphospha) 2, 4-t-butylphospha).

Examples of the above-mentioned sulfur-based antioxidant include a dialkyl thiodipropionate compound such as dilauryl thiodipropionate, dimyristyl thiodipropionate or distearyl thiodipropionate, and a β -alkylmercaptopropionate compound of a polyhydric alcohol such as tetrakis [ methylene (3-dodecylthio) propionate ] methane.

< other Components >)

The colored curable resin composition of the present invention may contain additives known in the art such as fillers, other polymer compounds, adhesion promoters, light stabilizers, chain transfer agents, and the like, as needed.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-sulfanylpropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, N-2- (aminoethyl) -3-aminopropyl methyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyl methyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyl trimethoxysilane, N-2- (aminoethyl) -3-aminopropyl methyldiethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane and N-phenyl-3-aminopropyl triethoxysilane.

Method for producing colored curable resin composition

The colored curable resin composition can be prepared, for example, by mixing the colorant (a), the resin (B), the solvent (E), and the leveling agent (F), and further mixing the resulting mixture with the polymerizable compound (C), the polymerization initiator (D), the polymerization initiator auxiliary (D1), and other components when patterning by photolithography.

The colored curable resin composition may be prepared by mixing the colorant (a), the resin (B) and the solvent (E) together to prepare a colored composition, and then mixing the colored composition with the polymerizable compound (C), the polymerization initiator (D), the polymerization initiator auxiliary (D1) and other components, and it is preferable to mix a part or all of the colorant (a) and the solvent (E) in advance and disperse the mixture to an average particle diameter of about 0.2 μm or less by a bead mill or the like. In this case, a part or all of the pigment dispersant and the resin (B) may be blended as necessary. The target colored curable resin composition can be prepared by mixing the remaining components in the pigment dispersion thus obtained to a predetermined concentration.

The dyes may be dissolved in a part or all of the solvent (E) respectively in advance to prepare solutions. The solution is preferably filtered through a filter having a pore size of about 0.01 μm to 1. Mu.m.

The mixed colored curable resin composition is preferably filtered through a filter having a pore diameter of about 0.1 μm to 10. Mu.m.

(3) Color filter

The 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 photolithography, inkjet method, and printing method. Among them, photolithography is preferable. Photolithography is a method of forming a colored curable composition layer by applying the colored curable composition to a substrate and drying the same, and exposing and developing the colored curable composition layer through a photomask. In the photolithography, a colored coating film which is a cured product of the colored curable resin composition layer can be formed without using a photomask and/or without developing at the time of exposure. The colored pattern and the colored coating film thus formed are the color filter of the present invention.

The film thickness of the color filter to be produced is not particularly limited, and may be appropriately adjusted depending on the purpose, application, and the like, and is, for example, 0.1 to 30. Mu.m, preferably 0.1 to 20. Mu.m, and more preferably 0.5 to 6. Mu.m.

As the substrate, a glass plate, a resin plate, silicon, a substrate on which aluminum, silver/copper/palladium alloy thin films, or the like is formed, or the like 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 photolithography can be performed by using a known or conventional apparatus and conditions. For example, the production can be performed as follows.

First, the colored curable resin composition is applied onto a substrate, and then dried by heating (prebaking) and/or drying under reduced pressure, thereby removing volatile components such as a solvent and drying the same to obtain a smooth colored curable resin composition layer.

Examples of the coating method include a spin coating method, a slit coating method, and a slit/spin coating method.

The temperature at which the heat drying is carried out is preferably 30 to 120 ℃, more preferably 50 to 110 ℃. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

In the case of drying under reduced pressure, it is preferable to carry out the drying under a pressure of 50 to 150Pa at a temperature of 20 to 25 ℃.

The film thickness of the colored curable resin composition is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

Next, the colored curable resin composition layer is exposed to light through a photomask for forming a target colored pattern. In order to uniformly irradiate the entire exposure surface with parallel light and to precisely align the photomask with the substrate on which the colored curable composition layer is formed, it is preferable to use an exposure device such as a mask aligner or stepper.

The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light of less than 350nm may be cut off using a filter that cuts off this wavelength region, or light of around 436nm, around 408nm, or around 365nm may be selectively extracted using a band-pass filter that extracts these wavelength regions. Specifically, mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like are cited.

The exposed colored curable composition layer is developed by contacting it with a developer, thereby forming a colored pattern on the substrate. The unexposed portion of the colored curable composition layer is dissolved in a developer and removed by development.

As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide is preferable. The concentration of the alkali compound in the aqueous solution may be, for example, 0.01 to 10 mass%. In addition, the developer may contain a surfactant.

The developing method may be any of paddle method, dipping method, spraying method, and the like. Further, the substrate can be inclined at an arbitrary angle during development.

The substrate after development is preferably washed with water.

It is further preferable to post-bake the resulting colored pattern.

(4) Display device

The above-described color filter is useful as a color filter used in a display device (e.g., a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state imaging element, among which the color filter is particularly used in an organic EL device.

Examples

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples, and may be carried out with appropriate modifications within the scope suitable for the above-described and the following gist, and these are included in the technical scope of the present invention. Hereinafter, "parts" means "parts by mass" and "%" means "% by mass" unless otherwise specified.

In the following synthesis examples, the structure of the compounds was confirmed by MASS spectrometry (LC; model 1200 by Agilent; model LC/MSD6130 by Agilent).

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

HLC-8120GPC (manufactured by Tosoh Co., ltd.)

Column TSK-GELG2000HXL

Column temperature of 40 DEG C

Solvent tetrahydrofuran

Flow Rate 1.0 mL/min

The concentration of the solid content of the analysis sample is 0.001 to 0.01 mass%

Sample injection amount 50. Mu.L

Detector RI

Standard substance for correction (TSK STANDARD PolySTYRENE F-40, F-4, F-288, A-2500, A-500, manufactured by Tosoh Corp.)

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

Synthesis example 1

8.0 parts of 3,4,9, 10-perylene tetracarboxylic dianhydride (manufactured by Tokyo chemical industries, ltd.), 8.7 parts of 6-aminoundecane (manufactured by Tokyo chemical industries, ltd.), 1.3 parts of zinc acetate (manufactured by Kao chemical industries, ltd.) and 314 parts of imidazole (manufactured by Tokyo chemical industries, ltd.) were added, and stirred at 150℃for 3 hours. 267 parts of 37% hydrochloric acid (manufactured by Kanto Kagaku Co., ltd.) and 1300 parts of water were added to the obtained mixture while keeping the temperature of the mixture at 20℃or lower, and as a result, orange-red precipitate was produced. The mixture containing the orange-red precipitate was filtered, and the residue after filtration was washed with 400 parts of water and 200 parts of methanol. The obtained residue was dried under reduced pressure at 60℃to obtain 12 parts (yield: 87%) of a compound represented by the formula (I-1).

< identification of Compound I-1 >

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 699

Accurate mass 698

Synthesis example 2

8.0 parts of 3,4,9, 10-perylene tetracarboxylic dianhydride (manufactured by Tokyo chemical industries, ltd.), 10 parts of 7-aminotridecane (manufactured by Tokyo chemical industries, ltd.), 1.3 parts of zinc acetate (manufactured by Kanto chemical industries, ltd.) and 314 parts of imidazole (manufactured by Tokyo chemical industries, ltd.) were added, and stirred at 150℃for 3 hours. 267 parts of 37% hydrochloric acid (manufactured by Kanto Kagaku Co., ltd.) and 1300 parts of water were added to the obtained mixture while keeping the temperature of the mixture at 20℃or lower, and as a result, orange-red precipitate was produced. The mixture containing the orange-red precipitate was filtered, and the residue after filtration was washed with 400 parts of water and 200 parts of methanol. The obtained residue was dried under reduced pressure at 60℃to obtain 12 parts of a compound represented by the formula (I-2) (yield 79%).

< identification of Compound I-2 >

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 755

Accurate mass 754

Compound (II-2) was obtained from Tokyo chemical industry Co.

Synthesis example 3

10 parts of 1,6,7, 12-tetrachloro-3, 4,9, 10-perylene dianhydride (Combinatorial Chemistry Co., ltd.), 13 parts of 2, 6-diisopropylaniline (Tokyo chemical industry Co., ltd.) and 188 parts of propionic acid were added, and stirred under reflux for 20 hours. 50 parts of water was added while keeping the temperature of the resulting mixture at 20℃or lower, resulting in an orange precipitate. The mixture containing the orange precipitate was filtered, and the residue after filtration was washed with 200 parts of water and 100 parts of methanol. The resulting residue was dried under reduced pressure at 60℃to give 12 parts of intermediate compound (INT) (yield 75%).

< identification of Compound INT >

Ionization mode=esi +: M/z= [ m+h ] +847.9

Accurate mass 848.6

5.0 parts of INT, 1.5 parts of 4-chlorophenol (manufactured by Tokyo chemical Co., ltd.), 3.1 parts of 4-tert-butylphenol (manufactured by Tokyo chemical Co., ltd.), 11 parts of potassium carbonate (manufactured by Kanto chemical Co., ltd.), and 295 parts of N-methylpyrrolidone (manufactured by Kanto chemical Co., ltd.) were added, and stirred at 130℃for 13 hours. 29 parts of 37% hydrochloric acid (manufactured by Kanto Kagaku Kogyo Co., ltd.) and 142 parts of water were added to the obtained mixture while keeping the temperature of the mixture at 20℃or lower, and as a result, a dark red precipitate was produced. The mixture containing the dark red precipitate was filtered, and the residue after filtration was washed with 300 parts of water and 150 parts of methanol. The obtained residue was dried under reduced pressure at 60℃to obtain 6.1 parts (yield: 81%) of a compound represented by the formula (II-92).

< identification of Compound II-92 >

Ionization mode=esi +: M/z= [ m+h ] +1237.8

Accurate mass 1236.8

Synthesis example 4

A flask equipped with a reflux condenser, a dropping funnel and a stirrer was charged with an appropriate amount of nitrogen and replaced with a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was charged, and the mixture was heated to 80℃with stirring. Next, 38 parts of acrylic acid, 3, 4-epoxytricyclo [5.2.1.0 ] was added dropwise over 5 hours ^2,6 ]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0 ² ^,6 ]Decane-9-yl ester (molar ratio 1:1) 289 parts, propylene glycol monomethyl ether acetate 125 parts. On the other hand, a solution obtained by dissolving 33 parts of 2, 2-azobis (2, 4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was kept at 80℃for 4 hours and then cooled to room temperature to obtain a copolymer (resin B1) solution having a solid content of 35.1% and a viscosity of 125 mPas as measured by a B-type viscometer (23 ℃). The resulting copolymer had a weight average molecular weight Mw of 9.2X10 ³ The dispersity was 2.08, and the acid value in terms of solid content was 77mg-KOH/g. The resin B1 has the following structural units.

Example 1 >

(1) Preparation of coloring composition

The respective components were mixed in the following proportions to obtain a coloring composition 1.

(2) Preparation of colored curable resin composition

Next, the respective components were mixed in the following proportions to obtain a colored curable resin composition 1.

Coloring composition 1:478

(C) Polymerizable Compound dipentaerythritol hexaacrylate

(Kayarad (registered trademark) DPHA; manufactured by Kayarad Co., ltd.) 40 parts

(D) Polymerization initiator N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF corporation) 2 parts

(F) 0.15 part of polyether modified organic silicone oil (Toray Silicone SH8400: dow Corning Toray (manufactured by Kabushiki Kaisha)) as a leveling agent

(3) Preparation of colored coating film

The colored curable resin composition was applied to a 5cm square glass substrate (EAGLE XG; manufactured by Corning) by spin coating so that the film thickness after post-baking was 1.7 to 2. Mu.m, and then pre-baked at 100℃for 3 minutes to form a colored curable resin composition layer. After cooling, the colored curable resin composition layer formed on the substrate was subjected to an exposure machine (TME-150 RSK; manufactured by TOPCON Co., ltd.) at 80mJ/cm under an atmospheric atmosphere ² The exposure amount (365 nm reference) of the substrate was irradiated with light. After the light irradiation, post-baking was performed in an oven at 230℃for 30 minutes to obtain a colored coating film.

(4) Test of Heat resistance

The xy chromaticity coordinates (x, Y) and Y of the resulting colored coating film were measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS). The colored coating film after measurement was heated in an oven at 230℃for 120 minutes under an air atmosphere. The xy chromaticity coordinates (x, Y) and Y after heating (230 ℃ C., 120 minutes) were measured using a colorimeter. The color difference Δe was calculated from the measured values before and after heating by the method described in JIS Z8730:2009 (calculation method for color difference) ^* ab。

The fluorescence intensity of the colored curable composition film before heating (230 ℃ C., 120 minutes) was measured using a fluorescence spectrophotometer (FluoMAX-3; manufactured by horiba, ltd.) (excitation side slit 5, fluorescence side slit 10, excitation wavelength 460 nm). The fluorescence intensity at a wavelength of 610nm was obtained, and the ratio of the fluorescence intensity to that before heating in comparative example 1 was obtained. The results are shown in Table 7.

Further, the fluorescence intensity of the colored curable composition film after heating (230 ℃ C., 120 minutes) was measured using a fluorescence spectrophotometer (FluoMAX-3; manufactured by horiba, ltd.) (excitation side slit 5, fluorescence side slit 10, excitation wavelength 460 nm). The fluorescence intensity at a wavelength of 610nm was obtained, and the ratio of the fluorescence intensity after heating to that of comparative example 1 was obtained. The results are shown in Table 7.

Example 2 >

A color curable resin composition 2 was obtained in the same manner as in example 1 except that the compound (I-2) was used in place of the compound (I-1) to prepare a colorant. The results are shown in Table 7.

Example 3 >

A color curable resin composition 3 was obtained in the same manner as in example 1 except that the compound (II-92) was used in place of the compound (II-2) to prepare a colorant. The results are shown in Table 7.

Example 4 >

A color curable resin composition 4 was obtained in the same manner as in example 2 except that the compound (II-92) was used in place of the compound (II-2) to prepare a colorant. The results are shown in Table 7.

Example 5 >

A color curable resin composition 5 was obtained in the same manner as in example 3 except that the amount of the compound (I-1) was changed from 1.3 parts to 2.6 parts and the amount of the compound (II-92) was changed from 2.6 parts to 1.3 parts. The results are shown in Table 7.

Comparative example 1 >

A color curable resin composition 6 was obtained in the same manner as in example 1 except that the compound (I-1) was not used to prepare a colorant. The results are shown in Table 7.

Comparative example 2 >

A color curable resin composition 7 was obtained in the same manner as in example 1 except that the compound (II-2) was changed from 2.6 parts to 3.9 parts and a colorant was prepared without using the compound (I-1). The results are shown in Table 7.

Comparative example 3 >

A color curable resin composition 8 was obtained in the same manner as in example 1 except that a coloring agent was prepared using Coumarin 545T (manufactured by tokyo chemical Co., ltd.) instead of the compound (I-1). The results are shown in Table 7.

Comparative example 4 >

A color curable resin composition 9 was obtained in the same manner as in comparative example 1 except that the compound (II-2) was replaced with the compound (II-92). The results are shown in Table 7.

TABLE 7

The coloring composition of the present invention has a color difference ΔE before and after the heat resistance test ^* Small ab and high fluorescence intensity after heat resistance test. Therefore, it can be understood that the coloring composition of the present invention is excellent in heat resistance.

Claims

1. A coloring composition comprising a colorant and a resin, wherein the colorant comprises a compound represented by the following formula (I) and a fluorescent dye, the fluorescent dye comprises a compound having a structure different from that of the compound represented by the formula (I), the compound having a structure different from that of the compound represented by the formula (I) is a red fluorescent dye,

in the formula (I) of the present invention,

R ¹ ～R ⁴ each independently represents an alkyl group having 5 to 10 carbon atoms,

R ⁵ ～R ¹² each independently represents a hydrocarbon group having 1 to 40 carbon atoms, a hydrogen atom, a halogen atom or a nitro group which may have a substituent,

the red fluorescent dye is a compound represented by the following formula (II),

in the formula (II) of the present invention,

Ar ¹ ～Ar ⁶ each independently represents an aryl group which may have a substituent,

2. A colored curable resin composition comprising a compound represented by the following formula (I), a fluorescent dye, a resin, a polymerizable compound, a polymerization initiator and a solvent, wherein the fluorescent dye contains a compound having a structure different from that of the compound represented by the formula (I), the compound having a structure different from that of the compound represented by the formula (I) is a red fluorescent dye,

In the formula (I) of the present invention,

in the formula (II) of the present invention,

R ¹⁵ ～R ¹⁸ each independently represent can have a fetchA hydrocarbon group having 1 to 40 carbon atoms, a hydrogen atom, a halogen atom or a nitro group.

3. A color filter formed from the colored curable resin composition according to claim 2.

4. A display device comprising the color filter of claim 3.