CN113056523A

CN113056523A - Coloring composition

Info

Publication number: CN113056523A
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: 2021-06-29
Anticipated expiration: 2039-11-11
Also published as: JP2020079397A; CN113056523B; KR20210088554A; TW202024079A; TWI811481B; 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, the colorant containing a compound represented by formula (I) and a fluorescent dye containing 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 colored composition, and further relates to a colored curable resin composition, a color filter, and a display device.

Background

In the field of organic semiconductor materials, materials containing perylene tetracarboxylic diimide compounds are known (patent document 1).

Documents of the prior art

Patent document

Patent document 1: international publication No. 2011/105152

Disclosure of Invention

In the field of colorants, colorants containing fluorescent dyes have been used, and a coloring composition containing such colorants is required to have improved heat resistance.

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

The invention provides the following colored composition, colored curable resin composition, color filter and display device.

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

[ in the formula (I),

R¹～R⁴each independently represents an alkyl group having 5 to 10 carbon atoms.

R⁵～R¹²Each independently represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a hydrogen atom, a halogen atom or a nitro group.]

[2] The coloring composition according to [1], wherein the compound having a structure different from that of the compound represented by the 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),

Ar¹～Ar⁶each independently represents an aryl group which may have a substituent.

R¹⁵～R¹⁸Each independently represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a hydrogen atom, a halogen atom or a nitro group.]

[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),

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

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

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

Detailed Description

(1) Coloring composition

The coloring composition of the present invention comprises 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 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 are preferably compounds having different structures (chemical structures) when represented by chemical formulas.

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 (a 1)).

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

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

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

< Compound (I) >)

R¹～R⁴The alkyl group has 5 to 10 carbon atoms, preferably 5 to 8 carbon atoms. R¹～R⁴The alkyl group represented by (a) may be linear, branched or cyclic, and is preferably linear.

As R¹～R⁴Examples of the straight-chain alkyl group include n-pentyl group,N-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl. 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 viewpoint of solubility in a solvent and fluorescence intensity.

As R¹～R⁴Examples of the branched alkyl group include a 1-methylbutyl group, a 1-methylpentyl group, a 1-methylhexyl group, a 1-methylheptyl group, a 1-methyloctyl group, a 1-methylnonyl group, a 1-ethylpropyl group, a 1-ethylbutyl group, a 1-ethylpentyl group, a 1-ethylhexyl group, a 1-ethylheptyl group, a 1-ethyloctyl group, a 2-methylbutyl group, a 2-methylpentyl group, a 2-methylhexyl group, a 2-methylheptyl group, a 2-methyloctyl group, a 2-methylnonyl group, a 2-ethylpropyl group, a 2-ethylbutyl group, a 2-ethylpentyl group, a 2-ethylhexyl group, a 2-ethylheptyl group, and a 2-ethyloctyl group.

As R¹～R⁴Examples of the cyclic alkyl group include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl.

R¹～R⁴Each of the alkyl groups may be independently a group obtained by combining a linear alkyl group and a cyclic alkyl group, or a group obtained by combining a branched alkyl group and a cyclic alkyl group. The number of carbon atoms of the group obtained by combining these groups may be 5 to 10.

R¹～R⁴May be of the same kind or of different kinds, preferably of the same kind.

As R¹～R⁴Specific examples of (A) include groups represented by the following formulae. Denotes the bonding site.

As R⁵～R¹²Examples of the halogen atom include fluorine atomChlorine atom, bromine atom, iodine atom and the like. Among them, fluorine atom and chlorine atom are preferable.

As R⁵～R¹²Examples of the hydrocarbon group having 1 to 40 carbon atoms include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The aliphatic hydrocarbon group may be saturated or unsaturated, or may be linear or cyclic.

As R⁵～R¹²Examples of the saturated or unsaturated chain aliphatic hydrocarbon group include straight-chain alkyl groups such as 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, hentriacontyl, dotriacontyl, tritriacontyl, tetratriacontyl, pentadecanyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, and forty-alkyl groups; 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, isohexyl, (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, 2-pentenyl and the like; and the like. The number of carbon atoms of the saturated or unsaturated chain hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 15, and particularly preferably 1 to 10. Among them, 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 R⁵～R¹²Examples of the saturated or unsaturated alicyclic hydrocarbon group include cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclohexyl, and 2-Cycloalkyl groups such as 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, 2,4, 6-trimethylcyclohexyl, 2,6, 6-tetramethylcyclohexyl, 3,5, 5-tetramethylcyclohexyl, 4-pentylcyclohexyl, 4-octylcyclohexyl, 4-cyclohexylcyclohexyl and the like; cycloalkenyl groups such as cyclohexenyl (e.g., cyclohex-2-ene, cyclohex-3-ene), cycloheptene, and cyclooctene; 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, and particularly preferably 5 to 10. Among them, most preferred is cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

As R⁵～R¹²The aromatic hydrocarbon group may include a phenyl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, a 2-ethylphenyl group, a 3-ethylphenyl group, a 4-ethylphenyl group, a 2, 3-dimethylphenyl group, a 2, 4-dimethylphenyl group, a 2, 5-dimethylphenyl group, a 2, 6-dimethylphenyl group, a 3, 4-dimethylphenyl group, a 3, 5-dimethylphenyl group, a 4-vinylphenyl group, an o-isopropylphenyl group, a m-isopropylphenyl group, a p-isopropylphenyl group, an o-tert-butylphenyl group, a m-tert-butylphenyl group, a p-tert-butylphenyl group, a 3, 5-di (tert-butyl) phenyl group, a trimethylphenyl group, a 4-ethylphenyl group, a 4-butylphenyl group, a 4-pentylphenyl group, a 2, 6-bis (2-propyl) phenyl group, a 4-cyclohexylphenyl group, a 2,4, 6-trimethylphenyl group, a 4-octylphenyl group, a, And aromatic hydrocarbon groups such as 1-naphthyl, 2-naphthyl, 5,6,7, 8-tetrahydro-1-naphthyl, 5,6,7, 8-tetrahydro-2-naphthyl, fluorenyl, phenanthryl, anthracyl, 2-dodecylphenyl, 3-dodecylphenyl, 4-dodecylphenyl, and pyrenyl. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and further preferablyThe selection is 6-15.

R⁵～R¹²The hydrocarbon group represented may be a group obtained by combining 2 or more of the above-mentioned hydrocarbon groups, and for example, an aromatic hydrocarbon group and at least one of a chain hydrocarbon group and an alicyclic hydrocarbon group may be combined, and examples thereof include an aralkyl group such as a benzyl group, a phenethyl group, and a 1-methyl-1-phenylethyl group; an arylalkenyl group such as a phenylvinyl group (phenylvinyl group); arylalkynyl groups such as phenylethynyl; a phenyl group having 1 or more phenyl groups bonded thereto, such as a biphenyl group and a terphenyl group; cyclohexylmethylphenyl, benzylphenyl, (dimethyl (phenyl) methyl) phenyl, and the like.

R⁵～R¹²The hydrocarbon group represented may be a group obtained by combining 2 or more of the above-mentioned hydrocarbon groups, and examples thereof include a group obtained by combining a chain hydrocarbon group and an alicyclic hydrocarbon group, and examples thereof include an alkyl group to which 1 or more alicyclic hydrocarbon groups are bonded, such as a cyclopropylmethyl group, a cyclopropylethyl group, a cyclobutylmethyl group, a cyclobutylethyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, a 2-methylcyclohexylmethyl group, a cyclohexylethyl group, and an adamantylmethyl group.

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

As R⁵～R¹²Examples of the substituent which may be contained in the hydrocarbon group having 1 to 40 carbon atoms 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-COR¹²、－COOR¹³、－OCOR¹³、－OR¹³、－SR¹³、－SOR¹³、－SO₂R¹³、－SO₂NHR¹³、－SO₂NR¹³R¹⁴、－CONHR¹³、－CONR¹³R¹⁴、－NHR¹³、－NR¹³R¹⁴、－NHCOR¹³、－NR¹⁴COR¹³And the like.

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

R¹³And R¹⁴Each independently represents an alkyl group, a phenyl group or a naphthyl group.

R¹³And R¹⁴The 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 a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group.

as-COR¹³Examples thereof include acetyl, propionyl, butyryl, 2-dimethylpropionyl, pentanoyl, hexanoyl, (2-ethyl) hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, heneicosanoyl, and benzoyl.

as-COOR¹³Examples thereof include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, pentoxycarbonyl, hexyloxycarbonyl, (2-ethyl) hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, undecyloxycarbonyl, dodecyloxycarbonyl, phenoxycarbonyl and eicosyloxycarbonyl.

as-OCOR¹³Examples thereof include acetoxy, propionyloxy, butyryloxy, 2-dimethylpropionyloxy, valeryloxy, hexanoyloxy, (2-ethyl) hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy, decanoyloxy, undecanoyloxy, dodecanoyloxy, heneicosanoyloxy, benzoyloxy, vinylcarbonyloxy, 2-propenylcarbonyloxy and the like.

as-OR¹³Examples thereof include methoxy, ethoxy, propoxy, butoxy, pentyloxy, phenoxy and naphthyloxy.

As a-SR¹³Examples thereof include methylsulfanyl, ethylsulfanyl, propylsulfanyl, butylsulfanyl, t-butylsulfanyl, pentylsulfanyl, hexylsulfanyl, (2-ethyl) hexylsulfanyl, heptylsulfanyl, octylsulfanyl, nonylsulfanyl, decylthanyl, undecylsulfanyl, dodecylsulfanyl, eicosylsulfanyl, phenylsulfanyl, and o-tolylsulfanyl.

as-SOR¹³Examples thereof include methylsulfinyl, ethylsulfinyl, propylsulfinyl, butylsulfinyl, pentylsulfinyl, phenylsulfinyl and naphthylsulfinyl groups.

as-SO₂R¹³Examples thereof include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, pentylsulfonyl, phenylsulfonyl, naphthylsulfonyl and the like.

as-SO₂NHR¹³Examples thereof include N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl, 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 and N-phenylsulfamoyl.

as-SO₂NR¹³R¹⁴Examples thereof include N, N-dimethylsulfamoyl, N-ethylmethylsulfamoyl, N-diethylsulfamoyl, N-propylmethylsulfamoyl, N-dipropylsulfamoyl, N-isopropylmethylsulfamoyl, N-diisopropylsulfamoyl, N-tert-butylmethylsulfamoyl, N-diisobutylsulfamoyl, N-di-sec-butylsulfamoyl, N-di-tert-butylsulfamoyl, N-butylmethylsulfamoyl, N-dibutylsulfamoyl, N-dipentylsulfamoyl, N-di (1-ethylpropyl) sulfamoyl, N-diethylsulfamoyl, N-diisopropylsulfamoyl, N,N, N-dihexylsulfamoyl, N-di (2-ethyl) hexylsulfamoyl, N-diheptylsulfamoyl, N-octylmethylsulfamoyl, N-dioctylsulfamoyl, N-dinonylsulfamoyl, N-decylmethylsulfamoyl, N-undecylmethylsulfamoyl, N-dodecylmethylsulfamoyl, N-eicosylmethylsulfamoyl, N-phenylmethylsulfamoyl, N-diphenylsulfamoyl, etc.

as-CONHR¹³Examples thereof include N-methylcarbamoyl, N-ethylcarbamoyl, N-propylcarbamoyl, N-isopropylcarbamoyl, N-butylcarbamoyl, N-isobutylcarbamoyl, N-sec-butylcarbamoyl, N-tert-butylcarbamoyl, N-pentylcarbamoyl, N- (1-ethylpropyl) carbamoyl, N-hexylcarbamoyl, N- (2-ethyl) hexylcarbamoyl, N-heptylcarbamoyl, N-octylcarbamoyl, N-nonylcarbamoyl, N-decylcarbamoyl, N-undecylcarbamoyl, N-dodecylcarbamoyl, N-eicosylcarbamoyl and N-phenylcarbamoyl.

as-CONR¹³R¹⁴Examples thereof include an N, N-dimethylcarbamoyl group, an N, N-ethylmethylcarbamoyl group, an N, N-diethylcarbamoyl group, an N, N-propylmethylcarbamoyl group, an N, N-dipropylcarbamoyl group, an N, N-isopropylmethylcarbamoyl group, an N, N-diisopropylcarbamoyl group, an N, N-tert-butylmethylcarbamoyl group, an N, N-diisobutylcarbamoyl group, an N, N-di-sec-butylcarbamoyl group, an N, N-di-tert-butylcarbamoyl group, an N, N-butylmethylcarbamoyl group, an N, N-dibutylcarbamoyl group, an N, N-butyloctylcarbamoyl group, an N, N-dipentylcarbamoyl group, an N, N-di (1-ethylpropyl) carbamoyl group, an N, N-dihexylcarbamoyl group, an N, N-di (2-ethyl) hexylcarbamoyl group, N, N-diheptylcarbamoyl, N-octylmethylcarbamoyl, N-dioctylcarbamoyl, N-dinonylcarbamoyl, N-decylmethylcarbamoyl, N-undecylmethylcarbamoylAcyl, N-dodecylmethylcarbamoyl, N-eicosylmethyl carbamoyl, N-phenylmethylcarbamoyl, N-diphenylcarbamoyl and the like.

as-NHR¹³Examples 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 and N-phenylamino.

as-NR¹³R¹⁴Examples thereof include N, N-dimethylamino group, N-ethylmethylamino group, N-diethylamino group, N-propylmethylamino group, N-dipropylamino group, N-isopropylmethylamino group, N-diisopropylamino group, N-tert-butylmethylamino group, N-diisobutylamino group, N-di-sec-butylamino group, N-di-tert-butylamino group, N-butylmethylamino group, N-dibutylamino group, N-dipentylamino group, N-bis (1-ethylpropyl) amino group, N-dihexylamino group, N-bis (2-ethyl) hexylamino group, N-diheptylamino group, N-dioctylamino group, N-dinonylamino group, N-decylmethylamino group, N-undecylmethylamino group, N-dodecylmethylamino group, N, N-eicosylmethyl amino, N-phenylmethyl amino, N-diphenylamino and the like.

as-NHCOR¹³Examples thereof include acetylamino, propionylamino, butyrylamino, 2-dimethylpropionylamino, pentanoylamino, hexanoylamino, (2-ethyl) hexanoylamino, heptanoylamino, octanoylamino, nonanoylamino, decanoylamino, undecanoylamino, dodecanoylamino, heneicosanoylamino, benzoylamino and the like.

as-NR¹⁴COR¹³Examples thereof include N-methyl-N-acetylamino and the like.

R⁵～R¹²Carbon of-CH containing in a hydrocarbon group having 1 to 40 carbon atoms and not constituting a ring₂May be substituted by-O-, -CO-, -S (O)₂－、－NR^x1-. wherein-CH₂-not by substitution, -COOH and-S (O)₂OH。R^x1Represents 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 a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and an isopentyl group.

As R⁵～R¹²Examples thereof include groups represented by the following formulae. Denotes the bonding site.

As R⁵～R¹²Preferred groups are hydrogen atom, halogen atom, hydroxyl group, nitro group, cyano group, -CH₃And 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, R⁵～R¹²Preferably a hydrogen atom.

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

[ Table 1]

R¹

R²

R³

R⁴

R⁵

R⁶

R⁷

R⁸

R⁹

R¹⁰

R¹¹

R¹²

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

A preferred embodiment of the compound (I) in the present invention includes a compound represented by the following formula (I-1) (hereinafter, also referred to as compound (I-1)).

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

The compound (I) can be produced, for example, by reacting a compound represented by the following formula (pt1) with a compound represented by the following formula (n1) in a solvent.

[ in the formula, R⁵～R¹²As defined above.]

H₂NCHR¹R² (n1)

[ in the formula, R¹And R²As defined above.]

Examples of the compound represented by the formula (pt1) include 3,4,9, 10-perylenetetracarboxylic dianhydride and the like.

Examples of the compound represented by the formula (n1) include 1-pentylhexylamine (6-aminoundecane) and 1-hexylheptylamine (7-aminotridecane). The compound represented by the formula (n1) may be used alone, or 2 or more compounds may be used.

The amount of the compound represented by the formula (n1) used is usually 1 to 10 moles, preferably 1 to 8 moles, more preferably 1 to 6 moles, and still more preferably 1 to 4 moles, based on 1 mole of the compound represented by the formula (pt 1).

As the solvent, for example, 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 dichloromethane, chloroform, and 1, 2-dichlorobenzene; amide solvents such as N, N-dimethylformamide and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide.

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

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

After the reaction is completed, the method for removing compound (I) is not particularly limited, and it can be removed by various known methods. For example, the compound (I) can 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 reaction is completed, the compound (I) can be removed by filtration. After filtration, the obtained residue may be purified by column chromatography, recrystallization, or the like. The chemical structure of the obtained compound (I) can be analyzed by a known analytical 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, an elemental analysis method, and the like. The X-ray crystal structure analysis method can be performed, 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-perylenetetracarboxylic dianhydride with 1-hexylheptylamine in a solvent.

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

< fluorescent dye (a) >

The fluorescent dye (a) is a dye having a fluorescent property (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),

R¹⁵～R¹⁸Each independently represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a hydrogen atom, a halogen atom or a nitro group.

As Ar¹～Ar⁶Examples of the aryl group include phenyl and naphthyl. AsAr¹～Ar⁶Aryl groups represented by (a) are preferably phenyl groups.

As Ar¹～Ar⁶The substituent that the aryl group may have includes a substituent 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 arylamine group, an aralkylamino group, an alkylamino group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, an aralkenyl group, a heterocyclic group having 3 to 10 carbon atoms, and an ethynyl group. Among them, an alkyl group having 1 to 10 carbon atoms and a halogen atom 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.

Ar¹～Ar⁶The aryl group may have 1 or 2 or more substituents, or may have none.

As Ar¹～Ar⁶Examples thereof include groups represented by the following formulae. Denotes the bonding site.

As Ar¹～Ar⁶Preferred substituents are those represented by the formulae (E-1), (E-4), (E-7), (E-9), (E-17), (E-18) and (E-19). With these groups, the fluorescence intensity tends to be high. Ar (Ar)¹And Ar²Preferably the same. Ar (Ar)³～Ar⁶The same type or different types may be used.

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

[ Table 2]

Ar¹

Ar²

Ar³

Ar⁴

Ar⁵

Ar⁶

R¹⁵

R¹⁶

R¹⁷

R¹⁸

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]

Ar¹

Ar²

Ar³

Ar⁴

Ar⁵

Ar⁶

R¹⁵

R¹⁶

R¹⁷

R¹⁸

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]

Ar¹

Ar²

Ar³

Ar⁴

Ar⁵

Ar⁶

R¹⁵

R¹⁶

R¹⁷

R¹⁸

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]

Ar¹

Ar²

Ar³

Ar⁴

Ar⁵

Ar⁶

R¹⁵

R¹⁶

R¹⁷

R¹⁸

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]

Ar¹

Ar²

Ar³

Ar⁴

Ar⁵

Ar⁶

R¹⁵

R¹⁶

R¹⁷

R¹⁸

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

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

Another preferred embodiment of the compound (II) in the present invention includes compounds represented by the following formulae (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 (pt2), a compound represented by the following formula (AR1), and a compound represented by the following formula (AR2) in a solvent.

[ in the formula, R⁵～R¹²As defined above.]

Ar－NH₂ (AR1)

Ar－OH (AR2)

[ wherein Ar is the same as Ar described above¹～Ar⁶The same definition is applied.]

Examples of the compound represented by the formula (pt2) include 1,6,7, 12-tetrachloroperylene tetracarboxylic dianhydride and the like.

Examples of the compound represented by formula (AR1) include 2, 6-diisopropylaniline, aniline, 3, 5-dimethylaniline, and 3, 5-di-tert-butylaniline. The compound represented by the formula (AR1) may be used alone, or 2 or more compounds may be used.

Examples of the compound represented by formula (AR2) include phenol, 4-fluorophenol, 4-chlorophenol, and 4-bromophenol. The compound represented by the formula (AR1) may be used alone, or 2 or more compounds may be used.

The total amount of the compound represented by formula (AR1) and the compound represented by formula (AR2) to be used is usually 1 to 10 mol, preferably 1 to 8 mol, more preferably 1 to 6 mol, and still more preferably 1 to 4 mol, based on 1 mol of the compound represented by formula (pt 2).

As the solvent, water may be mentioned; 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 dichloromethane, 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 and butyric acid, and imidazole. N-methylpyrrolidone, imidazole and propionic acid are preferred.

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

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

After the reaction is completed, the method for removing the compound (II) is not particularly limited, and the compound (II) can be removed by various known methods. For example, the compound (II) can 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 reaction is completed, the compound (II) can be removed by filtration. After filtration, the obtained residue may be purified by column chromatography, recrystallization, or the like. The chemical structure of the obtained compound (II) can be analyzed by a known analytical 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, an elemental analysis method, and the like. The X-ray crystal structure analysis method can be performed, 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.

As typical commercially available products of the compound (II-2), Lumogen (registered trademark) F Red 305 and the like can be cited.

< colorant (A) >)

The lower limit of the content of the compound (I) in the colorant (a) may be, for example, 0.1 mass% or more, 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, with respect to the total amount of the colorant (a).

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

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, based on the total amount of the colorant (a).

The lower limit of the content of the fluorescent dye (a) in the colorant (a) may be, for example, 0.1 mass% or more, 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, with respect to the total amount of the colorant (a).

On the other hand, the upper limit of the content of the fluorescent dye (a) in the colorant (a) may be, for example, 99.9 mass% or less with respect to the total amount of the colorant (a), 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.

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, based on 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, further preferably 5% by mass or more, particularly preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 50% by mass or more, particularly preferably 70% by mass or more, and very preferably 90% by mass or more, based on 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 extremely preferably 10% by mass or less, based on 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 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%, 1 mass% or more, 5 mass% or more, 10 mass%, 20 mass%, 50 mass%, 70 mass%, 90 mass%, or the like, based on 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, for example, 99.9 mass% or less with respect to the total amount of the colorant (a), and specific examples thereof may be 99.5 mass%, 99 mass%, 95 mass%, 90 mass%, 80 mass%, 50 mass%, 30 mass%, 10 mass%, and the like.

When the colorant (a) contains the compound (I) and the fluorescent dye (a), the fluorescence intensity of the fluorescent dye (a) tends to increase.

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, the heat resistance and the 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, based on 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 excluding all solvent components from the coloring composition. The total amount of solid components and the contents of the respective components 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, known dyes can be used, and for example, known dyes described in The color index (published by The Society of Dyers and Colourists) and dyeing guidelines (chromo). Further, depending on the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, anthraquinone dyes, naphthoquinone dyes, quinonimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, phthalocyanine dyes, perylene dyes, and the like can be given. These dyes may be used alone or in combination of 2 or more.

Specific examples thereof include the following color index (c.i.) numbered dyes.

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. solvent orange 2, 7, 11, 15, 26, 41, 54, 56, 77, 86, 99;

c.i. solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

c.i. solvent blue 4,5, 14, 18, 35, 36, 37, 38, 44, 45, 58, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;

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

c.i. acid yellow 1,3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

c.i. acid red 1,4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;

c.i. acid orange 6,7,8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 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, 90:1, 91, 92, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 243, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 267, 296, 278, 285, 340, 285, 340;

c.i. acid dyes such as c.i. acid green 1,3,5, 6,7,8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50:1, 58, 63, 65, 80, 104, 105, 106, 109 and the like,

c.i. direct yellow 2,4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;

c.i. direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

c.i. direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

c.i. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

c.i. direct blue 1,2,3,6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 87, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 256, 236, 229, 237, 242, 244, 245, 247, 238, 248, 250, 257, 275, 260, 251, 293, 268, 274, 251, 268;

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

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

c.i. disperse violet 26, 27;

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

c.i. basic red 1, 10;

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

c.i. basic violet 2;

c.i. basic red 9;

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

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

c.i. reactive orange 16;

C.I. reactive dyes such as C.I. reactive red 36,

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

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

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

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

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

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

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

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) may be mentioned.

As The pigment, known pigments can be used, and for example, pigments classified as pigments (pigments) in The color index (published by The Society of Dyers and Colourists) can be cited. These may be used alone, or 2 or more of them may be used in combination.

Specifically, there may be mentioned 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 and the like;

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

red pigments such as c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 178, 179, 180, 190, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273 and the like;

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

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

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

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

c.i. pigment black 1, 7, 31, 32 and the like.

The colorant (a1) may be subjected to, if necessary, rosin treatment, surface treatment using a derivative or the like into which an acidic group or a basic group has been introduced, grafting treatment on the surface of the colorant (a1) by a polymer compound or the like, microparticulation treatment by a sulfuric acid microparticulation method or the like, cleaning treatment by an organic solvent, water or the like for removing impurities, removal treatment by an ion exchange method or the like for removing ionic impurities, or the like. 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 content of the total amount 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, further 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 content of the total amount of the compound (I) and the compound (II) in the colorant (a) is usually less than 100% by mass relative to the total amount of the colorant (a).

When the colorant (a) further contains a colorant (a1), the content of the colorant (a) in the coloring composition is usually 0.1 to 99% by mass, for example, 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, based on the total amount of solid components in the coloring composition.

When the coloring composition contains the solvent (E), a coloring composition can 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 and mixing the colorant (a) in the solvent (E). The solution containing the colorant may contain a part or all of the solvent (E) contained in the coloring composition.

The content of the solid content in the colorant-containing solution is preferably 0.01 to 99.99% by mass, more preferably 0.1 to 99.9% by mass, even more preferably 0.1 to 99% by mass, even more preferably 1 to 90% by mass, even more preferably 1 to 60% by mass, even more preferably 3 to 50% by mass, particularly preferably 3 to 30% by mass, and very preferably 5 to 30% by mass, based on 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 to 99.9999% by mass, more preferably 0.01 to 99% by mass, still more preferably 0.1 to 99% by mass, particularly preferably 1 to 99% by mass, and still more preferably 2 to 99% by mass, of 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) in the colorant-containing solution. The total amount of solid components and the contents of the respective components relative to the total amount can be measured by a known analytical method such as liquid chromatography or gas chromatography.

As for the colorant (a1), the colorant (a1) can be brought into a state of being uniformly dispersed in the solution containing the colorant (a1) by performing a dispersion treatment with a dispersant. 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, there may be mentioned polyester, polyamide, acrylic and other surfactants. These dispersants may be used alone or in combination of two or more. Examples of the dispersant include KP (manufactured by shin-Etsu chemical industry Co., Ltd.), FLOWLEN (manufactured by Kyoho chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca), EFKA (registered trademark) (manufactured by BASF), AJISPER (registered trademark) (manufactured by AJIAOSU Fine chemical Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), BYK (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), and the like.

When a dispersant is used for the preparation of the colorant-containing solution, the amount of the dispersant (solid content) 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 used is within the above range, a more uniformly dispersed solution containing the colorant 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 an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride.

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

Examples of the other structural units include structural units derived from a monomer copolymerizable with the monomer (a) (which is different from the monomer (a) and the monomer (b) and may be referred to as "monomer (c)" hereinafter), structural units 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;

carboxyl group-containing bicyclic unsaturated compounds such as 5-norbornene-2, 3-dicarboxylic acid methyl ester, 5-carboxybicyclo [2.2.1] hept-2-ene, 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxymethylbicyclo [2.2.1] hept-2-ene and 5-carboxyethylbicyclo [2.2.1] hept-2-ene;

carboxylic acid anhydrides such as anhydrides of the above unsaturated dicarboxylic acids excluding fumaric acid and methylfumaric acid;

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

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

Among them, acrylic acid, methacrylic acid, 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 oxirane 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 ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (b 1)"), a monomer having an oxetanyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (b 2)"), a monomer having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (b 3)"), and the like.

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

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

Specific examples of the monomer (b 1-1) include glycidyl (meth) acrylate, β -methylglycidyl (meth) acrylate, β -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, vinylbenzyl glycidyl ether, α -methylvinylbenzyl 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, and the like.

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

[ formula (BI) and formula (BII) wherein R^aAnd R^bEach 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^aAnd X^bEach independently represents a single bond, [ R ]^c－、*－R^c－O－、*－R^c-S-or R^c－NH－。

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

Denotes the bonding site to O. ]

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

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

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

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

As X^aAnd X^bPreferred examples thereof include a single bond, methylene, ethylene and-CH₂-O-and-CH₂CH₂More preferably, the group-O-includes a single bond and-CH₂CH₂-O- (. indicates a bonding site to O.).

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

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

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

As the monomer (b2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable.

Examples of the monomer (b2) include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxyethyloxetane, 3-methyl-3-acryloxyethyloxetane, 3-ethyl-3-methacryloxyethyloxetane, and 3-ethyl-3-acryloxyethyloxetane.

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

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

The monomer (b) is preferably the monomer (b1) in view of enabling the obtained color filter to have higher reliability such as heat resistance, chemical resistance and the like. Further, the monomer (b 1-2) is more preferable in terms of excellent storage stability of the coloring composition.

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

hydroxyl 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-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2 '-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5, 6-dihydroxybicyclo [2.2.1] hept-2-ene, 5, 6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-bis (2' -hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-dimethoxybicyclo [ 2.1] hept-2-ene, 5, 6-bis (2.1) hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxyhept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-2.1 ] hept-2, Bicyclic unsaturated compounds such as 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonybicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5, 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5, 6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;

dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate and N- (9-acridinyl) maleimide;

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

Among them, styrene, vinyltoluene, and tricyclo [5.2.1.0 ] meth (acrylic acid) are preferable from the viewpoint of copolymerization reactivity and heat resistance^2,6]Decan-8-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid)² _, ⁶]Decan-9-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decen-8-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decen-9-yl ester, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1]Hept-2-ene, 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 monomer (a) and the monomer (b) and an ethylenically unsaturated bond to a polymer having a structural unit derived from the monomer (a) and the monomer (b).

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

The polymer having a structural unit derived from the monomer (a) can be produced, for example, by polymerizing a monomer constituting the structural unit of the polymer in a solvent in the presence of a polymerization initiator. The polymerization initiator, the solvent and the like are not particularly limited, and those generally used in the art can be used. Examples of the polymerization initiator include azo compounds (e.g., 2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), and organic peroxides (e.g., benzoyl peroxide), and any solvent may be used as long as it dissolves the monomers.

The polymer obtained may be used as it is in the solution after the reaction, may be used as it is, may be used as a concentrated or diluted solution, or may be used as it is taken out as a solid (powder) by a method such as reprecipitation.

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

Examples of the carboxylic acid 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-dicarboxybicyclo [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 [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(meth) acrylic acid copolymer, glycidyl (meth) acrylate/(benzyl (meth) acrylate/(meth) acrylic acid copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, and 3, 4-epoxytricyclo [5.2.1.0 ] meth) acrylic acid^2,6]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(meth) acrylic acid/vinyltoluene copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(meth) acrylic acid 2-ethylhexyl ester copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(meth) acrylic acid tricyclo [5.2.1.0^2,6]Decenyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane/(meth) acrylic acid/styrene copolymer, benzyl (meth) acrylate/(meth) acrylic acid copolymer, styrene/(meth) acrylic acid copolymer) Acrylic copolymers, and resins described in each of Japanese patent application laid-open Nos. 9-106071, 2004-29518, and 2004-361455.

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

The resin (B) may be used in combination of 2 or more, and in this case, the resin (B) preferably contains at least one member selected from the group consisting of 3, 4-epoxytricyclo [5.2.1.0 ] s of (meth) acrylic acid^2,6]Decyl ester/(meth) acrylic acid copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(meth) acrylic acid/vinyltoluene copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]1 or more of decyl ester/(meth) acrylic acid 2-ethylhexyl ester copolymer.

The weight average molecular weight (Mw) of the resin (B) in terms of polystyrene is preferably 1000 to 100000, more preferably 1000 to 50000, still more preferably 1000 to 30000, and 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, and still more preferably 1.01 to 4.

The acid value (solid content equivalent value) of the resin (B) is preferably from 10 mg-KOH/g to 300 mg-KOH/g, more preferably from 20 mg-KOH/g to 250 mg-KOH/g, still more preferably from 20 mg-KOH/g to 200 mg-KOH/g, particularly preferably from 20 mg-KOH/g to 170 mg-KOH/g, still more preferably from 30 mg-KOH/g to 170 mg-KOH/g, particularly preferably from 60 mg-KOH/g to 150 mg-KOH/g, and very preferably from 65 mg-KOH/g to 135 mg-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 determined, for example, by titration with an aqueous solution of potassium hydroxide.

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 a solution containing a colorant after preparing the solution containing a colorant in advance, the solution containing a colorant may contain a part or all, preferably a part, of the resin (B) described later contained in the coloring composition in advance. By containing the resin (B) in advance, the dispersion stability of the solution containing the colorant can be further improved.

The content of the resin (B) in the colorant-containing solution may be, for example, 10000 parts by mass or less, preferably 5000 parts by mass or less, more preferably 1000 parts by mass or less, still more preferably 1 to 500 parts by mass, particularly preferably 5 to 200 parts by mass, and still more 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), the colorant (a) containing 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), the colorant (a) containing 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, sometimes referred to as a polymerizable compound (C)), and a polymerization initiator (hereinafter, sometimes 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 a leveling agent (F)), an antioxidant (hereinafter, sometimes referred to as an antioxidant (G)), and a solvent (E).

The content of the solid content 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, and the like required for curing the colored curable resin composition, and may be, for example, 1 to 99% by mass, preferably 1 to 90% by mass, more preferably 2 to 80% by mass, further preferably 3 to 70% by mass, particularly preferably 4 to 60% by mass, further preferably 5 to 50% by mass, particularly preferably 6 to 45% by mass, and extremely preferably 7 to 40% by mass, based on the total amount of the solid content in the colored curable resin composition.

The content of the colorant (a) in the colored curable resin composition is not particularly limited since it is appropriately adjusted according to the chromaticity, brightness, film thickness, and the like required for curing the colored curable resin composition, 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, of the total amount of solid components in the colored curable resin composition.

In the present specification, the "total amount of solid components in the colored curable resin composition" refers to the total amount of components excluding the solvent (E) from the colored curable resin composition. The total amount of solid components and the contents of the respective components 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 content in the colored curable resin composition may be, for example, 0.01% by mass or more and less than 100% by mass, preferably 0.1% by mass to 99.9% by mass, more preferably 0.1% by mass to 99% by mass, still more preferably 1% by mass to 90% by mass, particularly preferably 1% by mass to 60% by mass, still more preferably 3% by mass to 50% by mass, still more preferably 3% by mass to 30% by mass, and particularly preferably 5% by mass to 30% by mass, based on the total amount of the colored curable resin composition.

The colored pattern and the colored coating film formed from the colored curable resin composition of the present invention, which will be described later, tend to have high fluorescence intensity at a wavelength of 610nm in addition to excellent heat resistance, and it is preferable that the fluorescent pattern and the colored coating film formed from the colored curable resin composition containing the fluorescent dye (a) alone have higher fluorescence intensity at a wavelength of 610 nm. The fluorescence intensity can be measured, for example, using a fluorescence spectrophotometer (FluoroMAX-3; manufactured by horiba, Ltd.).

< polymerizable Compound (C) >)

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

Examples of the polymerizable compound having 1 ethylenically unsaturated bond include nonylphenylcarbinol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, 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 Esters and the like are preferably dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

The weight average molecular weight of the polymerizable compound (C) is preferably 50 to 4000, more preferably 50 to 3500, still more 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, relative to 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 an active radical, an acid, or the like under the action of light or heat to initiate polymerization, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include an O-acyloxime compound, an alkylphenone compound, a bisimidazole compound, a triazine compound, and an acylphosphine oxide compound.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-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-dioxopentylmethyloxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-imine and N-benzoyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-one-2-imine, etc. Further, as the O-acyloxime compound, commercially available products such as Irgacure OXE01, OXE02 (both of which are manufactured by BASF) and N-1919 (manufactured by ADEKA Co., Ltd.) 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 alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, and 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [ 4- (4-morpholino) phenyl ] butan-1-one. As the alkylphenone compound, commercially available products such as Irgacure 369, 907 and 379 (all of which are manufactured by BASF) can be used.

Examples of the alkylphenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [ 4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone and benzildimethylketal.

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

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, and the like.

Examples of the acylphosphine oxide compound include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide and the like. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) 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 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone and 2,4, 6-trimethylbenzophenone; quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl benzoylformate, titanocene compounds, and the like.

These are preferably used in combination with a polymerization initiation aid (D1) (particularly an amine) described later.

The polymerization initiator (D) is preferably a polymerization initiator containing at least 1 selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a bisimidazole 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 the polymerizable compound (C) contained in the colored curable resin composition.

< polymerization initiation assistant (D1) >)

The polymerization initiation aid (D1) is a compound or sensitizer for promoting polymerization of a polymerizable compound whose polymerization is initiated 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 initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N-dimethyl-p-toluidine, 4 '-bis (dimethylamino) benzophenone (commonly known as michelson), 4' -bis (diethylamino) benzophenone, and 4,4 '-bis (ethylmethylamino) benzophenone, and 4, 4' -bis (diethylamino) benzophenone is preferable. As the amine compound, a commercially available compound such as EAB-F (manufactured by UK 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 phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylsulfanylacetic acid, N-naphthylglycine, and naphthyloxyacetic acid.

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

< solvent (E) >

Examples of the solvent (E) include an ester solvent (a solvent containing-COO-and not containing-O-in the molecule), an ether solvent (a solvent containing-O-and not containing-COO-in the molecule), an ether ester solvent (a solvent containing-COO-and not containing-COO-in the molecule), a ketone solvent (a solvent containing-CO-and not containing-COO-in the molecule), an alcohol solvent (a solvent containing OH and not containing-O-, -CO-, and-COO-, a solvent), an aromatic hydrocarbon solvent, an amide solvent, and dimethyl sulfoxide.

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

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

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

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

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

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

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

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

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

The content of the solvent (E) is usually 99.99% by mass or less, preferably 0.1% by mass to 99.9% by mass, more preferably 1% by mass to 99.9% by mass, even more preferably 10% by mass to 99% by mass, particularly preferably 40% by mass to 99% by mass, even more preferably 50% by mass to 97% by mass, particularly preferably 70% by mass to 97% by mass, and very preferably 70% by mass to 90% by mass, based on 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 content 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, yet more preferably 3 to 50% by mass, and particularly preferably 3 to 30% by mass, based on 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, further preferably 5% by mass or more, further preferably 10% by mass or more, and further preferably 15% by mass or more of 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% by mass, for example, may be 99% by mass or less, based on the total amount of solid components in the colorant-containing solution.

When the compound (I) and all or a part of the fluorescent dye (a) are dispersed in all or a part of the solvent (E) to prepare a solution containing the colorant, the dispersion stability of the solution containing the colorant 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, for example, 10000 parts by mass or less, preferably 5000 parts by mass or less, more preferably 1000 parts by mass or less, still more preferably 1 to 500 parts by mass, particularly preferably 5 to 200 parts by mass, and still more 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, if necessary, rosin treatment, surface treatment using a derivative or the like into which an acidic group or a basic group is introduced, grafting treatment of the surfaces of the compound (I) and the fluorescent dye (a) with a polymer compound or the like, microparticulation treatment by a sulfuric acid microparticulation method or the like, cleaning treatment by an organic solvent, water or the like for removing impurities, removal treatment by an ion exchange method or the like for removing ionic impurities, or the like. 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 dispersed by a dispersing agent to a state where the compound (I) and the fluorescent dye (a) are uniformly dispersed in a solution containing a colorant. The compound (I) and the fluorescent dye (a) may be dispersed separately or in combination of two or more. When the colorant (a) contains the compound (I), the fluorescent dye (a) and the dispersant, the dispersibility of the compound (I) is improved, and the heat resistance tends to be easily improved.

When the dispersant is used, the amount of the dispersant (solid content) used is 10000 parts by mass or less, preferably 5000 parts by mass or less, more preferably 1000 parts by mass or less, further preferably 500 parts by mass or less, particularly preferably 300 parts by mass or less, further preferably 100 parts by mass or less, further preferably 5 to 100 parts by mass, and particularly preferably 5 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 used is within the above range, a more uniformly dispersed solution containing the colorant 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 a silicone surfactant, a fluorine surfactant, and a silicone surfactant having a fluorine atom. These may have a polymerizable group in a side chain.

Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: manufactured by Dow Corning corporation), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by shin-Etsu chemical industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by MONTMEIVE PERFURIACE MATLS. MATPANI contract Co., Ltd.) may be mentioned.

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

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

When the leveling agent (F) is contained, the content thereof is usually 0.0005 to 5% by mass, preferably 0.001 to 1% by mass, more preferably 0.001 to 0.5% by mass, and still more preferably 0.005 to 0.1% by mass, based on 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 industrially commonly used antioxidant, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like can be used.

Examples of the above-mentioned phenolic antioxidants include Irganox 1010(Irganox 1010: pentaerythritol tetrakis [ 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], manufactured by BASF), Irganox 1076(Irganox 1076: octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, manufactured by BASF), Irganox 1330(Irganox 1330:3,3 ', 5,5 ' -hexa-t-butyl-a, a ' - (mesitylene-2, 4, 6-triyl) tri-p-cresol, manufactured by BASF), Irganox 3114(Irganox 3114:1,3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1, 3, 5-triazine-2, 4,6(1H, 3H, 5H) -trione, manufactured by BASF), Irganox 3790(Irganox 3790:1,3, 5-tri-t-butyl-4-hydroxybenzyl) -1, 3, 5-triazine-2, 4,6(1H, 5H) -trione, manufactured by BASF), 3, 5-triazine-2, 4,6(1H, 3H, 5H) -trione, manufactured by BASF), Irganox 1035(Irganox 1035: thiodiethylene bis [ 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], manufactured by BASF), Irganox1135 (Irganox1135: phenylalanic acid, 3, 5-bis (1, 1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, manufactured by BASF), Irganox 1520L (Irganox 1520L:4, 6-bis (octylthiomethyl) -o-cresol, manufactured by BASF), Irganox 3125(Irganox 3125, manufactured by BASF), Irganox 565(Irganox 565:2, 4-bis (n-octylthio) -6- (4-hydroxy 3 ', 5' -di-tert-butylanilino) -1, 3, 5-triazine, manufactured by BASF), ADK B80 (ADK B80: ADK 3-bis (ADK 3-5-hydroxy propionyloxy) -1, 3, 5-bis (ADB 3-5-hydroxy-phenyl-5-methyl-o-phenyl-5, 1-dimethylethyl) -2, 4,8, 10-tetraoxaspiro (5,5) undecane (manufactured by ADEKA), Sumilizer BHT (Sumilizer BHT, manufactured by Sumitomo chemical Co., Ltd.), Sumilizer GA-80 (Sumilizer GA-80, manufactured by Sumitomo chemical Co., Ltd.), Sumilizer GS (Sumilizer GS, manufactured by Sumitomo chemical Co., Ltd.), Cyanox 1790 (manufactured by Sitech)) and vitamin E (manufactured by Eisai).

Examples of the phosphorus-based antioxidant include Irgafos 168(Irgafos 168: tris (2, 4-di-t-butylphenyl) phosphite, manufactured by BASF), Irgafos 12(Irgafos 12: tris [ 2- [ [2,4,8, 10-tetra-t-butylbenzo [ d, f ] [1,3,2] dioxaphosphin-6-yl ] oxy ] ethyl ] amine, manufactured by BASF), Irgafos 38(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), ADSTAB PEP-8 ((manufactured by ADEKA), Sandstab P-EPQ (manufactured by Clariant), Weston618 (GE, manufactured by Weston618, manufactured by Wemilstin), Wemilstin 626 (manufactured by Westin G619, manufactured by Westin 626, manufactured by Westin GK-6-hydroxy propoxy 3- (GP-3, manufactured by Westin) (manufactured by Westin) and U.3- (3-butyl) propoxy G, manufactured by BASF) -2, 4,8, 10-tetra-tert-butyldibenzo [ d, f ] [1.3.2] dioxaphosphepin) (manufactured by Sumitomo chemical Co., Ltd.), and the like.

Examples of the sulfur-based antioxidant include dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and β -alkylmercaptopropionate compounds of polyhydric alcohols such as tetrakis [ methylene (3-dodecylthio) propionate ] methane.

< other ingredients >

The colored curable resin composition of the present invention may contain additives known in the art, such as a filler, another polymer compound, an adhesion promoter, a light stabilizer, and a chain transfer agent, as required.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-thioalkylpropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-glycidyloxy-3-epoxysilane, and the like, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltriethoxysilane, etc.

< 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 mixture with the polymerizable compound (C), the polymerization initiator (D), the polymerization initiation aid (D1), and other components when the pattern is formed 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 initiation aid (D1) and other components, and it is preferable that the colorant (a) and the solvent (E) are mixed in advance in part or in whole, and dispersed by a bead mill or the like until the average particle size of the pigment becomes about 0.2 μm or less. In this case, a part or all of the pigment dispersant and the resin (B) may be blended as necessary. The remaining components are mixed in the thus obtained pigment dispersion liquid so as to have a predetermined concentration, whereby the target colored curable resin composition can be prepared.

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

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

(3) Color filter

The color filter can be formed from the colored curable resin composition of the present invention. Examples of a method for forming a colored pattern include a photolithography method, an ink jet method, a printing method, and the like. Among them, photolithography is preferable. The photolithography method is a method in which the colored curable composition is applied to a substrate and dried to form a colored curable composition layer, and the colored curable composition layer is exposed to light through a photomask and developed. In the photolithography method, a colored coating film which is a cured product of the colored curable resin composition layer can be formed without using a photomask and/or without performing development at the time of exposure. The colored pattern and the colored coating film formed in this way are the color filter of the present invention.

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

As the substrate, a glass plate, a resin plate, silicon, a substrate in which a thin film of aluminum, silver/copper/palladium alloy, or the like is formed on the substrate, 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 following can be used.

First, a substrate is coated with the colored curable resin composition, and is dried by heating (prebaking) and/or drying under reduced pressure to remove volatile components such as a solvent and dry the composition, thereby obtaining 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 for heating and drying is preferably 30 to 120 ℃, more preferably 50 to 110 ℃. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

When the drying is carried out under reduced pressure, the drying is preferably carried out under a pressure of 50 to 150Pa and at a temperature of 20 to 25 ℃.

The film thickness of the 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 parallel light rays to the entire exposure surface and perform precise alignment of the photomask and the substrate on which the colored curable composition layer is formed, an exposure apparatus such as a mask aligner or a stepper is preferably used.

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

The exposed colored curable composition layer is brought into contact with a developer to develop the layer, thereby forming a colored pattern on the substrate. The unexposed portion of the colored curable composition layer is dissolved in a developing solution and removed by development.

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

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

The developed substrate is preferably washed with water.

Further preferably, the obtained colored pattern is subjected to post-baking.

(4) Display device

The color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, or the like) and a solid-state imaging element, and particularly as a color filter used in an organic EL device.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples, and it goes without saying that the present invention can be carried out with appropriate modifications within a range that can be adapted to the gist described above and below, and these are included in the technical scope of the present invention. In the following, unless otherwise specified, "part" means "part by mass" and "%" means "% by mass".

In the following synthesis examples, the structure of the compound was confirmed by MASS spectrometry (LC; model 1200 by Agilent, MASS; 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-8120 GPC (manufactured by Tosoh corporation)

The column is TSK-GELG 2000HXL

Column temperature 40 deg.C

Solvent tetrahydrofuran

Flow rate 1.0 mL/min

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

Sample size 50 μ L

Detector RI

Calibration standard materials TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh corporation)

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

Synthesis example 1

8.0 parts of 3,4,9, 10-perylenetetracarboxylic dianhydride (manufactured by Beijing chemical industry Co., Ltd., Bay.) and 8.7 parts of 6-aminoundecane (manufactured by Tokyo chemical industry Co., Ltd.), 1.3 parts of zinc acetate (manufactured by Kanto chemical industry Co., Ltd.) and 314 parts of imidazole (manufactured by Tokyo chemical industry Co., Ltd.) were added thereto, and the mixture was stirred at 150 ℃ for 3 hours. While the resulting mixture was kept at 20 ℃ or lower, 267 parts of previously prepared 37% hydrochloric acid (manufactured by Kanto chemical Co., Ltd.) and 1300 parts of water were added to the mixture, whereby an orange-red precipitate was produced. The mixture containing the orange-red precipitate was filtered, and the filtered residue 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-1) (yield 87%).

< identification of Compound I-1 >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺699

Accurate mass 698

Synthesis example 2

8.0 parts of 3,4,9, 10-perylenetetracarboxylic 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 thereto and stirred at 150 ℃ for 3 hours. While the resulting mixture was kept at 20 ℃ or lower, 267 parts of previously prepared 37% hydrochloric acid (manufactured by Kanto chemical Co., Ltd.) and 1300 parts of water were added to the mixture, whereby an orange-red precipitate was produced. The mixture containing the orange-red precipitate was filtered, and the filtered residue was washed with 400 parts of water and 200 parts of methanol. The obtained residue was dried at 60 ℃ under reduced pressure to obtain 12 parts of a compound represented by the formula (I-2) (yield 79%).

< identification of Compound I-2 >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺755

Accurate mass 754

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

Synthesis example 3

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

< identification of Compound INT >

(Mass analysis) ionization mode ESI +: M/z ═ M + H ] +847.9

Accurate mass 848.6

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

< identification of Compound II-92 >

(Mass analysis) ionization mode ESI + (M/z ═ M + H ] +1237.8

Accurate mass 1236.8

Synthesis example 4

An appropriate amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the atmosphere was changed to a nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was charged and heated to 80 ℃ with stirring. Then, 38 parts of acrylic acid and 3, 4-epoxytricyclo [5.2.1.0 ] acrylic acid were added dropwise over 5 hours^2,6]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0² ^,6]A mixed solution of 289 parts of a mixture of decane-9-yl esters (containing 1:1 ratio in terms of molar ratio) and 125 parts of propylene glycol monomethyl ether acetate. On the other hand, 33 parts of 2, 2-azobis (2, 4-dimethylvaleronitrile) was added dropwise over 6 hours to dissolveThe resulting solution was dissolved in 235 parts of propylene glycol monomethyl ether acetate. After completion of the dropwise addition, the mixture was held at 80 ℃ for 4 hours and then cooled to room temperature to obtain a copolymer (resin B1) solution containing 35.1% of a solid content and having a viscosity of 125 mPas as measured with a type B viscometer (23 ℃). The weight-average molecular weight Mw of the resulting copolymer was 9.2X 10³The dispersion degree was 2.08, and the acid value in terms of solid content was 77 mg-KOH/g. The resin B1 has the following structural units.

< example 1 >

(1) Preparation of coloring composition

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 at the following ratio to obtain a colored curable resin composition 1.

1478 parts of coloring composition

(C) The polymerizable compound dipentaerythritol hexaacrylate

(KAYARAD (registered trademark) DPHA; manufactured by JAPONIC CHEMICAL DRUG, Ltd.) 40 parts

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

(F) Leveling agent 0.15 part of polyether-modified Silicone oil (Toray Silicone SH8400, manufactured by Dow Corning Toray Co., Ltd.)

(3) Production of colored coating film

The colored curable resin composition is applied onto a 5cm square glass substrate (EAGLE XG; manufactured by CORNING) by spin coating so that the post-baking film thickness is 1.7 to 2 μm, and then pre-baked at 100 ℃ for 3 minutes to form a colored cured productA layer of a sexual resin composition. After cooling, the colored curable resin composition layer formed on the substrate was exposed to an exposure machine (TME-150 RSK; manufactured by TOPCON, Inc.) at a thickness of 80mJ/cm in an atmospheric atmosphere²The exposure amount (365nm basis) of (A) was irradiated with light. After the light irradiation, the resultant was postbaked at 230 ℃ for 30 minutes in an oven to obtain a colored coating film.

(4) Heat resistance test

The xy chromaticity coordinates (x, Y) and Y of the obtained colored coating film were measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS). The colored coating film after the measurement was heated in an oven at 230 ℃ for 120 minutes in an air atmosphere. The xy chromaticity coordinates (x, Y) and Y after heating (230 ℃ C., 120 minutes) were measured using a color measuring machine. From the measurement values before and after heating, the color difference Δ E was calculated by the method described in JIS Z8730:2009(7. method for calculating color difference)^*ab。

The fluorescence intensity of the colored curable composition film before heating (230 ℃ C., 120 minutes) was measured using a fluorescence spectrophotometer (FluoroMAX-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 before heating to that of 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 (FluoroMAX-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 colored curable resin composition 2 was obtained in the same manner as in example 1, except that a colorant was prepared using the compound (I-2) in place of the compound (I-1). The results are shown in Table 7.

< example 3 >

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

< example 4 >

A colored curable resin composition 4 was obtained in the same manner as in example 2, except that a colorant was prepared using the compound (II-92) instead of the compound (II-2). The results are shown in Table 7.

< example 5 >

A colored 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 colored curable resin composition 6 was obtained in the same manner as in example 1, except that a colorant was prepared without using the compound (I-1). The results are shown in Table 7.

< comparative example 2 >

A colored 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 that a colorant was prepared without using the compound (I-1). The results are shown in Table 7.

< comparative example 3 >

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

< comparative example 4 >

A colored 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 colored composition of the present invention has a color difference Δ E before and after a heat resistance test^*ab is small, and the fluorescence intensity after the heat resistance test also tends to be high. 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 coloring agent and a resin, the coloring agent containing a compound represented by the following formula (I) and a fluorescent dye containing a compound having a structure different from that of the compound represented by the formula (I),

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

R¹～R⁴each independently represents an alkyl group having 5 to 10 carbon atoms,

R⁵～R¹²each independently represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a hydrogen atom, a halogen atom or a nitro group.

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

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

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

Ar¹～Ar⁶each independently represents an aryl 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), the compound is shown in the specification,

5. A color filter comprising the colored curable resin composition according to claim 4.

6. A display device comprising the color filter according to claim 5.