WO2019163732A1

WO2019163732A1 - Compound and coloring resin composition

Info

Publication number: WO2019163732A1
Application number: PCT/JP2019/005970
Authority: WO
Inventors: 佳亮井上; 裕河西; 哲郎赤坂
Original assignee: 住友化学株式会社
Priority date: 2018-02-26
Filing date: 2019-02-19
Publication date: 2019-08-29

Abstract

The present invention addresses the problem of providing a novel squarylium dye which enables a coloring resin composition to achieve chromaticity values equivalent to those of coloring resin compositions that contain conventional squarylium dyes even if the amount of the squarylium dye contained therein is small. The present invention is characterized by a compound represented by formula (I). (In formula (I), each of R¹-R⁴ independently represents a hydrogen atom or the like; each of R⁵-R⁸ independently represents a hydrogen atom or the like; each of R⁹ and R¹⁰ independently represents a monovalent saturated hydrocarbon group having 1-20 carbon atoms, or the like; each of R¹¹ and R¹² independently represents a halogen atom or a halogenated alkyl group having 1-6 carbon atoms; and each of m1 and m2 independently represents an integer of 1-5.)

Description

Compound and colored resin composition

The present invention relates to a novel compound and a colored resin composition.

It is known that squarylium dye is used as a colorant in a colored curable resin composition. Patent Document 1 proposes a squarylium dye represented by a specific general formula.

JP2015-86379A

An object of the present invention is to provide a novel squarylium dye that can achieve an equivalent chromaticity value even in the case of a colored resin composition having a low content of squarylium dye as compared with a colored resin composition containing a conventional squarylium dye. Is to provide. Another object of the present invention is to provide a novel squarylium dye precursor and a method for producing the same.

The present invention provides the following [1] to [6].
[1] A compound represented by the formula (I).

[In the formula (I),
R ¹ to R ⁴ each independently represents a hydrogen atom, a halogen atom, a hydroxy group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is a halogen atom , A hydroxy group or —N (R ^a ) ₂ may be substituted, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced with —O— or —S—. R ^a represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ⁵ to R ⁸ each independently represents a hydrogen atom or a hydroxy group.
R ⁹ and R ¹⁰ each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group includes a halogen atom, a hydroxy group, —N (R ^b ) ₂ or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group is —O—, — S—, —NR ^b — or —C (═O) — may be substituted. R ^b represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ¹¹ and R ¹² each independently represents a halogen atom or a halogenated alkyl group having 1 to 6 carbon atoms.
m1 and m2 each independently represents an integer of 1 to 5. When m1 is 2 or more, the plurality of R ¹¹ may be the same or different, and when m2 is 2 or more, the plurality of R ¹² may be the same or different. ]
[2] A colored resin composition comprising a colorant comprising the compound according to [1] and a resin.
[3] A color filter formed from the colored resin composition according to [2].
[4] A solid-state imaging device including the color filter according to [3].
[5] A method for producing the compound according to [1],
A compound represented by the following formula (IV-1) is reacted with 3,4-dihydroxy-3-cyclobutene-1,2-dione, or a compound represented by the following formula (IV-1) and 3, 4-dihydroxy-3-cyclobutene-1,2-dione is reacted, and the resulting compound represented by the following formula (V-1) and the compound represented by the following formula (IV-2) are reacted. ,Production method.

[In formula (IV-1), formula (V-1), and formula (IV-2),
R ¹ to R ⁴ each independently represents a hydrogen atom, a halogen atom, a hydroxy group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is a halogen atom , A hydroxy group or —N (R ^a ) ₂ may be substituted, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced with —O— or —S—. R ^a represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ⁵ to R ⁸ each independently represents a hydrogen atom or a hydroxy group.
R ⁹ and R ¹⁰ each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group includes a halogen atom, a hydroxy group, —N (R ^b ) ₂ or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group is —O—, — S—, —NR ^b — or —C (═O) — may be substituted. R ^b represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ¹¹ and R ¹² each independently represents a halogen atom or a halogenated alkyl group having 1 to 6 carbon atoms.
m1 and m2 each independently represents an integer of 1 to 5. When m1 is 2 or more, the plurality of R ¹¹ may be the same or different, and when m2 is 2 or more, the plurality of R ¹² may be the same or different. ]

[6] A compound represented by the formula (IV-1) described in [5].

The colored resin composition containing the compound represented by the formula (I) may reduce the content of the colorant when achieving the same chromaticity value as compared with the colored resin composition containing the conventional squarylium dye. it can. When the content of the colorant in the colored resin composition is reduced, the cured product of the obtained colored resin composition can be made into a thin film, and the range of design possibilities for the resin used in the colored resin composition is expanded. .

<Compound>
The compound of the present invention is a compound represented by formula (I) (hereinafter also referred to as compound (I)). In addition to the notation represented by the formula (I), the compound (I) includes tautomers having a resonance structure represented by the following formula, for example, and the compound (I) has all tautomers. Contains the body.

In the formula (I), examples of the halogen atom in R ¹ to R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ¹ to R ⁴ 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, and a nonyl group. Linear alkyl groups having 1 to 20 carbon atoms such as decyl, dodecyl, hexadecyl and icosyl; isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl and 2- A branched alkyl group having 3 to 20 carbon atoms such as ethylhexyl group; alicyclic saturation having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group A hydrocarbon group is mentioned.

Examples of the group in which the hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ¹ to R ⁴ is replaced with a halogen atom, a hydroxy group, or —N (R ^a ) ₂ include the following formulas: The group represented by these is mentioned. Here, as —N (R ^a ) ₂ , methylamino group, ethylamino group, n-propylamino group, n-butylamino group, n-pentylamino group, dimethylamino group, diethylamino group, dibutylamino group, Examples thereof include a methylethylamino group. Two R ^{a s} may be the same or different. In the following formula, * represents a bond.

Examples of the group in which —CH ₂ — in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ¹ to R ⁴ is replaced by —O— or —S— include groups represented by the following formulae: Is mentioned. In the following formula, * represents a bond.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁹ and R ¹⁰ 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, and a nonyl group. Linear alkyl groups having 1 to 20 carbon atoms such as decyl, dodecyl, hexadecyl and icosyl; isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl and 2- A branched alkyl group having 3 to 20 carbon atoms such as ethylhexyl group; alicyclic saturation having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group A hydrocarbon group is mentioned.

Examples of the group in which the hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁹ and R ¹⁰ is replaced with a halogen atom, a hydroxy group, or —N (R ^b ) ₂ include, for example, the following formulae: The group represented by these is mentioned. Here, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned. As —N (R ^b ) ₂ , —NHCH ₃ , —NHCH ₂ CH ₃ , —NHCH ₂ CH ₂ CH ₃ , —NHCH ₂ CH ₂ CH ₂ CH ₃ , —N (CH ₃ ) ₂ , —N (CH ₂ CH ₃ ) ₂ , —N (CH ₂ CH ₂ CH ₃ ) ₂ , —N (CH ₂ CH ₂ CH ₂ CH ₃ ) _{2 and the} like. The two R ^{b s} may be the same or different. In the following formula, * represents a bond.

A hydrogen atom contained in a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁹ and R ¹⁰ may be substituted, and an optionally substituted aromatic hydrocarbon having 6 to 20 carbon atoms Examples of the group include compounds represented by the following formula. In the following formula, * represents a bond.

A group in which a hydrogen atom contained in a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁹ and R ¹⁰ is substituted with an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms As, for example, a group represented by the following formula may be mentioned. In the following formula, * represents a bond.

—CH ₂ — contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁹ and R ¹⁰ is replaced with —O—, —S—, —NR ^b — or —C (═O) —. Examples of the group include a group represented by the following formula. In the following formula, * represents a bond.

As the halogen atom in R ¹¹ and R ^12, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the halogenated alkyl group having 1 to 6 carbon atoms in R ¹¹ and R ¹² include a fluorinated alkyl group having 1 to 6 carbon atoms, an alkyl chloride group, an alkyl bromide group, and an alkyl iodide group.

R ¹ to R ⁴ are preferably a hydrogen atom, a hydroxy group and a methyl group, more preferably a hydrogen atom.

As R ⁵ to R ⁸ , any one of R ⁵ and R ⁶ is preferably a hydroxy group, and any one of R ⁷ and R ⁸ is preferably a hydroxy group.

R ⁹ and R ¹⁰ are each an alkyl group having 4 to 10 carbon atoms (the hydrogen atom contained in the alkyl group may be substituted with a halogen atom or an optionally substituted carbon phenyl group). And —CH ₂ — contained in the alkyl group may be replaced by —O—, — or —C (═O) —), and is preferably an octyl group, nonyl group, decyl group, dodecyl group, 2 -Ethylhexyl group and the group shown below are more preferable,

2-ethylhexyl group and the following groups are more preferable.

R ¹¹ and R ¹² are preferably a fluorine atom or a fluorinated alkyl group having 1 to 6 carbon atoms, more preferably a fluorine atom or a trifluoromethyl group.

In formula (I),

A group represented by X ¹ , and

When the group represented by X ² is X ² , examples of the group represented by X ¹ and X ² include groups represented by the following formulas (A2-1) to (A2-36). * Represents a bond to a carbon atom.

Examples of the compound represented by the formula (I) include compounds (I-1) to (I-36) shown in Table 1 below. The following compounds also include compounds having all possible resonance structures.

Among these, from the viewpoint of raw material availability, it is represented by the following formulas (I-1), (I-7), (I-13), (I-19), (I-25), (I-31). Compounds are preferred.

Compound (I) of the present invention can be obtained, for example, by the method described in JP-A-2015-86379, a compound represented by the following formula (IV-1) and squaric acid (3,4-dihydroxy-3-cyclobutene-1,2 -Dione) (hereinafter also referred to as Method 1), or a compound represented by the following formula (IV-1) and 3,4-dihydroxy-3-cyclobutene-1,2-dione are reacted And the obtained compound represented by the following formula (V-1) and the compound represented by the following formula (IV-2) are reacted (hereinafter also referred to as method 2).

Examples of the compound represented by the formula (IV-1) include the following formulas (a-1-3), (a-7-3), (a-13-3), (a-19-3), ( Examples thereof include compounds represented by a-25-3) and (a-31-3).

In Method 1, the amount of squaric acid used is preferably 0.45 mol or more and 0.6 mol or less, more preferably 0.47 mol, per 1 mol of the compound represented by the formula (IV-I). It is 0.51 mol or less. In Method 2, the amount of squaric acid to be used is preferably 0.9 mol or more and 1.2 mol or less, more preferably 0.94 mol with respect to 1 mol of the compound represented by the formula (IV-I). It is 1.02 mol or more.

The reaction temperature is preferably 30 ° C to 180 ° C, more preferably 80 ° C to 140 ° C. The reaction time is preferably 1 hour to 20 hours, more preferably 3 hours to 15 hours.

The reaction is preferably performed in an organic solvent from the viewpoint of yield. Organic solvents include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; nitro hydrocarbon solvents such as nitrobenzene; methyl isobutyl Examples include ketone solvents such as ketones; amide solvents such as 1-methyl-2-pyrrolidone, and the like. Of these, a mixed solvent of butanol and toluene is preferable. The amount of the organic solvent to be used is preferably 5 parts by mass or more and 50 parts by mass or less, more preferably 10 parts by mass or more and 30 parts by mass or less with respect to 1 part by mass of the compound represented by the formula (IV-I). is there.

The method for obtaining the target compound (I-1) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, after cooling, a method of filtering the precipitated crystals can be mentioned. The crystals collected by filtration are preferably washed with water and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

The compound represented by the formula (IV-1) can be produced by reacting a compound represented by the following formula (IV-6) with boron tribromide. The compound represented by the following formula (IV-6) can be produced by reacting a compound represented by the following formula (IV-4) with a compound represented by the following formula (IV-5). . The compound represented by the following formula (IV-4) can be produced by reacting a compound represented by the following formula (IV-2) with a compound represented by the following formula (IV-3). .

[In the formula (IV-2),
R ¹¹ each independently represents a halogen atom or a halogenated alkyl group having 1 to 6 carbon atoms.
m1 independently represents an integer of 1 to 5. When m1 is 2 or more, the plurality of R ¹¹ may be the same or different. ]

[In the formula (IV-3),
R ¹ and R ² each independently represents a hydrogen atom, a halogen atom, a hydroxy group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is a halogen atom , A hydroxy group or —N (R ^a ) ₂ may be substituted, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced with —O— or —S—. R ^a represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
It may be one or different.
R ^5-1 and R ^6-1 independently represent a hydrogen atom, a hydroxy group or an alkoxy group having 1 to 20 carbon atoms, and at least one of R ^5-1 and R ^6-1 is a hydroxy group or a carbon number 1 to 20 alkoxy groups are represented. ]

[In the formula (IV-4),
R ¹ and R ² each independently represents a hydrogen atom, a halogen atom, a hydroxy group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is a halogen atom , A hydroxy group or —N (R ^a ) ₂ may be substituted, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced with —O— or —S—. R ^a represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ^5-1 and R ^6-1 independently represent a hydrogen atom, a hydroxy group or an alkoxy group having 1 to 20 carbon atoms, and at least one of R ^5-1 and R ^6-1 is a hydroxy group or a carbon number 1 to 20 alkoxy groups are represented.
R ¹¹ each independently represents a halogen atom or a halogenated alkyl group having 1 to 6 carbon atoms.
m1 independently represents an integer of 1 to 5. When m1 is 2 or more, the plurality of R ¹¹ may be the same or different. ]

[In the formula (IV-5),
R ⁹ each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is a halogen atom, a hydroxy group, —N (R ^b ) ₂ or The optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms may be substituted, and —CH ₂ — contained in the saturated hydrocarbon group may be —O—, —S—, —NR ^b — or —C (═O) — may be substituted. R ^b represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

[In the formula (IV-6),
R ¹ and R ² each independently represents a hydrogen atom, a halogen atom, a hydroxy group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is a halogen atom , A hydroxy group or —N (R ^a ) ₂ may be substituted, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced with —O— or —S—. R ^a represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ^5-1 and R ^6-1 independently represent a hydrogen atom, a hydroxy group or an alkoxy group having 1 to 20 carbon atoms, and at least one of R ^5-1 and R ^6-1 is a hydroxy group or a carbon number 1 to 20 alkoxy groups are represented.
R ⁹ each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is a halogen atom, a hydroxy group, —N (R ^b ) ₂ or The optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms may be substituted, and —CH ₂ — contained in the saturated hydrocarbon group may be —O—, —S—, —NR ^b — or —C (═O) — may be substituted. R ^b represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ¹¹ each independently represents a halogen atom or a halogenated alkyl group having 1 to 6 carbon atoms.
m1 independently represents an integer of 1 to 5. When m1 is 2 or more, the plurality of R ¹¹ may be the same or different. ]

Examples of the compound represented by the formula (IV-2) include 2,4-difluoroaniline, 2,5-difluoroaniline, 2,6-difluoroaniline, 2-trifluoromethylaniline represented by the following formula, 3- Examples thereof include trifluoromethylaniline, 4-trifluoromethylaniline and the like.

Examples of the compound represented by the formula (IV-3) include 3-bromoanisole represented by the following formula.

Examples of the compound represented by the formula (IV-4) include the following formulas (a-1-1), (a-7-1), (a-13-1), (a-19-1), ( a-25-1) and compounds represented by (a-31-1).

Examples of the compound represented by the formula (IV-5) include a compound represented by the following formula.

Examples of the compound represented by the formula (IV-6) include the following formulas (a-1-2), (a-7-2), (a-13-2), (a-19-2), ( a-25-2), (a-31-2) and the like.

As a method for producing the compound represented by the formula (IV-4) from the compound represented by the formula (IV-2) and the compound represented by the formula (IV-3), various known methods, For example, J. et al. Polymer Science Science Part A: Polymer Chemistry 2012, 50, 3788-3796, and methods described in JP 2016-11419 ([0140], [0150]).

As a method for producing the compound represented by the formula (IV-6) from the compound represented by the formula (IV-4) and the compound represented by the formula (IV-5), various known methods, For example, a method described in JP-A-2016-11419 ([0130]) can be mentioned.

As a method for producing the compound represented by the formula (IV-1) from the compound represented by the formula (IV-6) and boron tribromide, various known methods, for example, JP-A-2016-11419 ( [0132], [0152]).

<Colored resin composition>
The colored resin composition of the present invention includes a colorant (A) containing the compound of the present invention and a resin (B). In this specification, unless otherwise indicated, the compound illustrated as each component can be used individually or in combination of multiple types.

<Colorant (A)>
The colorant (A) may contain other dyes as the dye (A-1) in addition to the compound (I). Examples of such dyes include oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamides of acid dyes. For example, the Color Index (published by The Society of Dyers and Colorists) provides solvent and acid dyes. , Basic, reactive, direct, disperse, moldant, vat and the like, and known dyes described in Dyeing Notes (Color Dyeing). In addition, according to the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, and the like can be given. These dyes may be used alone or in combination of two or more.

Specifically, C.I. I. Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted, and only the number is described), 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82 83, 89, 94, 98, 99, 162;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56;
C. I. Solvent Red 24, 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 violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;
C. I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
C. I. Solvent Green 1, 3, 5, 28, 29, 32, 33; I. Solvent dyes,
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Acid 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 Red 73, 80, 91, 92, 97, 138, 151, 211, 274, 289;
C. I. Acid Green 3, 5, 9, 25, 27, 28, 41;
C. I. Acid Violet 34, 120;
C. I. Acid Blue 25, 27, 40, 45, 78, 80, 112; I. Acid dyes,

C. I. C. such as Basic Green 1; I. Basic dyes,

C. I. Reactive Yellow 2, 76, 116;
C. I. Reactive Orange 16; I. Reactive dyes,

C. I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;
C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct blue 40; I. Direct dyes,

C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse violet 26, 27;
C. I. Disperse Blue 1, 14, 56, 60; I. Disperse dyes,

C. I. As the mold dye, C.I. I. Moldant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; etc. . I. Moldant dyes,

C. I. C. of Bat Green 1 etc. I. Examples include vat dyes.

In the dye (A-1), the content of the compound (I) is preferably 3% by mass or more and 100% by mass or less, more preferably 10% by mass or more, based on the total amount of the dye (A-1). 70 mass% or less, more preferably 15 mass% or more and 50 mass% or less. When the content of the compound (I) is in the above range, high color reproducibility is obtained when it is used as a color filter, and the film tends to be thinned.

The colorant (A) preferably contains a pigment (A-2). The pigment (A-2) is not particularly limited, and a known pigment can be used. For example, pigments classified as pigments in the Color Index (published by The Society of Dyers and Colorists)
These can be used alone or in combination of two or more.
Examples of the pigment (A-2) include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, Yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. A brown pigment such as CI Pigment Brown 23, 25; I. And black pigments such as CI Pigment Black 1 and 7.

As pigment (A-2), C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 185, 194, 214; I. Green pigments such as C.I. Pigment Green 7, 36 and 58 are preferred; I. Pigment yellow 138, 150, 185 and C.I. I. Pigment Green 58 is more preferable, and C.I. I. Pigment yellow 138 and C.I. I. Pigment Green 58 is more preferable. By including the pigment, the transmission spectrum can be easily optimized, and the light resistance and chemical resistance of the color filter are improved.

If necessary, the pigment can be atomized by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment on the pigment surface with a polymer compound, sulfuric acid atomization method, etc. A treatment, a cleaning treatment with an organic solvent or water for removing impurities, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed.
The pigment preferably has a uniform particle size. By carrying out a dispersion treatment by containing a pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

Examples of the pigment dispersant include surfactants, and any of cationic, anionic, nonionic and amphoteric surfactants may be used. Specific examples include polyester-based, polyamine-based, acrylic-based surfactants, and the like. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Geneca Corporation), EFKA (registered trademark) (BASF) ), Ajisper (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by Big Chemie), and the like.
When a pigment dispersant is used, the amount used is preferably 1% by mass or more and 100% by mass or less, more preferably 5% by mass or more and 50% by mass or less, based on the total amount of the pigment (A-2). . When the amount of the pigment dispersant used is in the above range, there is a tendency that a pigment dispersion in a uniform dispersion state is obtained.

When the pigment (A-2) is contained, the content ratio of the dye (A-1) to the pigment (A-2) in the colorant (A) is usually from 45:55 to 1:99 on a mass basis. Yes, preferably 40:60 to 2:98, more preferably 38:62 to 3:97.

The content of the colorant (A) is preferably 5% by mass or more and 60% by mass or less, more preferably 8% by mass or more and 55% by mass or less, and still more preferably based on the total amount of the solid content. It is 10 mass% or more and 50 mass% or less. When the content of the colorant (A) is within the above range, the color density when it is used as a color filter is sufficient, and the resin (B) and the polymerizable compound (C) are contained in a necessary amount in the composition. Therefore, the film tends to be easily thinned. Here, the “total amount of solids” in this specification refers to an amount obtained by removing the content of the solvent from the total amount of the colored resin composition. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].
Resin [K1]; at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (Ba) (hereinafter also referred to as “(Ba)”), and 2 to 4 carbon atoms. A copolymer of a monomer (Bb) having a cyclic ether structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(Bb)”);
Resin [K2]; (Ba), (Bb), and monomer (Bc) copolymerizable with (Ba) (however, different from (Ba) and (Bb)) (hereinafter referred to as “(Bc)”) And a copolymer thereof);
Resin [K3]; Copolymer of (Ba) and (Bc);
Resin [K4]; a resin obtained by reacting (Bb) with a copolymer of (Ba) and (Bc);
Resin [K5]; a resin obtained by reacting (Ba) with a copolymer of (Bb) and (Bc);
Resin [K6]: a resin obtained by reacting a copolymer of (Bb) and (Bc) with (Ba) and further reacting with a carboxylic acid anhydride.

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

(Bb) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Say. (Bb) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

Examples of (Bb) include a monomer having an oxiranyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and an ethylenically unsaturated bond, and a tetrahydrofuryl group and an ethylenically unsaturated bond. And monomers.

(Bb) is preferably a monomer having an oxiranyl group and an ethylenically unsaturated bond from the viewpoint that the color filter to be obtained can have higher reliability such as heat resistance and chemical resistance. .

Examples of (Bc) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] Decane
8-yl (meth) acrylate (in this technical field, it is referred to as “dicyclopentanyl (meth) acrylate” as a common name. In some cases, it is also referred to as “tricyclodecyl (meth) acrylate”), tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (referred to in the art as “dicyclopentenyl (meth) acrylate”), dicyclopentanyl Such as oxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylic acid esters;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Of these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoints of copolymerization reactivity and heat resistance. preferable.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6. ] Resin such as decyl acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meta ) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- ( Resin [K2] such as (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; benzyl (meth) acrylate / Glycidyl (meth) acrylate was added to resin [K3]; benzyl (meth) acrylate / (meth) acrylic acid copolymer such as (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer Resin, tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer added with glycidyl (meth) acrylate, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic Resin with glycidyl (meth) acrylate added to acid copolymer

Resin [K4]; resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) Resin [K5] such as a resin obtained by reacting an acrylate copolymer with (meth) acrylic acid; (meth) acrylic acid reacted with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate Examples thereof include a resin [K6] such as a resin obtained by further reacting a resin with tetrahydrophthalic anhydride.
Especially, as resin (B), resin [K1] and resin [K2] are preferable.

For example, resin [K1] is a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) and the document Can be produced with reference to the cited references described in 1.

In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using the solvent contained in the colored resin composition of the present invention as a solvent during the polymerization, the solution after the reaction can be used as it is for the preparation of the colored resin composition of the present invention. The manufacturing process of the colored resin composition of the present invention can be simplified.

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. . When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film ratio is high, the solubility of the unexposed portion in the developer is good, and the resolution of the colored pattern tends to be improved.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

The acid value of the resin (B) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150, still more preferably 70 to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (B), and can be determined by titration with an aqueous potassium hydroxide solution, for example.

The content of the resin (B) is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, and further preferably 30 to 80% by mass with respect to the total amount of the solid content. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the remaining film rate tend to be improved.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond. Is a (meth) acrylic acid ester compound.

Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more of ethylenically unsaturated bonds. Examples of such polymerizable compounds include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the above-described (Ba) , Compounds having one ethylenically unsaturated bond, such as the compounds exemplified as (Bb) and (Bc);
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 Compounds having two ethylenically unsaturated bonds such as 3-methylpentanediol di (meth) acrylate;
Compounds having three ethylenically unsaturated bonds such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate;
It has four ethylenically unsaturated bonds such as pentaerythritol tetra (meth) acrylate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate and the like. Compound;
Compounds having 5 ethylenically unsaturated bonds such as dipentaerythritol penta (meth) acrylate;
Ethylenically unsaturated bonds such as dipentaerythritol hexa (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate A compound having six
Compounds having 7 or more ethylenically unsaturated bonds such as tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, etc. Is mentioned.
Among these, the polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds, and more preferably a polymerizable compound having 5 to 6 ethylenically unsaturated bonds. .
Of these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are particularly preferable.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 or more and 1,500 or less.

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass based on the total amount of the solid content. is there. When the content of the polymerizable compound (C) is within the above range, the remaining film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

The content ratio of the resin (B) to the polymerizable compound (C) [resin (B): polymerizable compound (C)] is preferably 20:80 to 80:20 on a mass basis, and more Preferably, it is 35:65 to 80:20.

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

The O-acyloxime compound is a compound having a partial structure represented by the formula (Dd1). Hereinafter, * represents a bond.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2, 4-Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1 [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methyl Benzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) may be used. Among them, O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1 At least one selected from the group consisting of -one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferred, and N-benzoyloxy -1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred. When these O-acyloxime compounds are used, a color filter with high brightness tends to be obtained.

The alkylphenone compound is a compound having a partial structure represented by the formula (Dd2) or a partial structure represented by the formula (Dd3). In these partial structures, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (Dd2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4 -Morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one Etc. Commercial products such as Irgacure 369, 907, 379 (above, manufactured by BASF) may be used.
Examples of the compound having a partial structure represented by the formula (Dd3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2 -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxy Examples include acetophenone and benzyl dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (Dd2).

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Styryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- 2-Methylfe Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, etc. .

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

Examples of the biimidazole compound include a compound represented by the formula (Dd4).

(Wherein R ^d1 to R ^d6 represent an aryl group having 6 to 10 carbon atoms which may have a substituent).

^Examples of the aryl group having 6 to 10 carbon atoms of R ^d1 to R ^d6 include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, and a naphthyl group, and is preferably a phenyl group.
Examples of the substituent which may be substituted for the aryl group of R ^d1 to R ^d6 include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example, Preferably it is a chlorine atom. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a methoxy group is preferable.

Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl). ) -4,4 ′, 5,5′-tetraphenylbiimidazole (for example, see JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2 ' -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (Thoria (Coxyphenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), a phenyl group at the 4,4 ′, 5,5′-position is substituted with a carboalkoxy group. Biimidazole compounds (see, for example, JP-A-7-10913). Among these, compounds represented by the following formula and mixtures thereof are preferable.

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

Examples of the polymerization initiator that generates an acid include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxy Onium salts such as phenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate And benzoin tosylate.

The polymerization initiator (D) is preferably a polymerization initiator that generates active radicals, and is at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds. Is more preferable, and a polymerization initiator including an O-acyloxime compound is more preferable.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, so the productivity of the color filter is improved.

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

Examples of the amine compound include alkanolamines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylbenzoate Aminobenzoic acid esters such as aminoethyl and 4-dimethylaminobenzoic acid 2-ethylhexyl; N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis ( Alkylaminobenzophenone such as diethylamino) benzophenone and 4,4′-bis (ethylmethylamino) benzophenone; and the like. Among them, alkylaminobenzophenone is preferable, and 4,4′-bis (diethylamino). Benzophenone is preferable. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

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

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

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, Examples thereof include N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

When these polymerization initiation assistants (D1) are used, the content thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). The amount is preferably 1 to 20 parts by mass. When the amount of the polymerization initiation assistant (D1) is within this range, a colored pattern can be formed with higher sensitivity and the productivity of the color filter tends to be improved.

<Solvent (E)>
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used individually or in combination of 2 or more types. For example, ester solvents (solvents containing —COO— in the molecule and not containing —O—), ether solvents (solvents containing —O— in the molecule and not containing —COO—), ether ester solvents (intramolecular Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O-,- Solvent containing no CO- and -COO-), aromatic hydrocarbon solvent, amide solvent, dimethyl sulfoxide and the like.

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

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

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

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

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

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

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

Of the above solvents, organic solvents having a boiling point of 120 ° C. or more and 210 ° C. or less at 1 atm are preferable from the viewpoint of coating properties and drying properties. Solvents include propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N-methylpyrrolidone and N, N-dimethylformamide are preferred, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 3-ethoxypropionic acid More preferred are ethyl, N-methylpyrrolidone and N, N-dimethylformamide.

The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the total amount of the colored resin composition of the present invention. In other words, the total solid content of the colored resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good. .

<Leveling agent (F)>
Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan GK) Can be mentioned.

Examples of the fluorosurfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), EFTOP (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) and E5844 (Daikin Fine Chemical Laboratory 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, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation), and the like can be given.

The content of the leveling agent (F) is preferably 0.0001% by mass or more and 0.2% by mass or less, more preferably 0.0002% by mass or more and 0.1% by mass with respect to the total amount of the colored resin composition. % Or less, and more preferably 0.0003 mass% or more and 0.05 mass% or less. This content does not include the content of the pigment dispersant. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>
The colored resin composition of the present invention contains additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., as necessary. But you can.

<Method for producing colored resin composition>
The colored resin composition of the present invention can be prepared, for example, by subjecting the colorant (A), the resin (B), the solvent (E), and the leveling agent (F) to patterning by a photolithographic method. It can be prepared by mixing together with the polymerization initiator (D), the polymerization initiation assistant (D1), and other components.
The pigment (A-2) is preferably mixed with a part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. The desired colored resin composition can be prepared by mixing the remaining components in the pigment dispersion thus obtained so as to have a predetermined concentration.
The dye may be previously dissolved in part or all of the solvent (E) to prepare a solution. The solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.
The mixed colored resin composition is preferably filtered with a filter having a pore size of about 0.1 to 10 μm.

<Color filter manufacturing method>
As a method for producing a color filter from the colored resin composition of the present invention, for example, a colored resin composition is applied on a substrate, and volatile components such as a solvent are removed by heat drying (prebaking) and / or drying under reduced pressure. And drying to form a smooth colored composition layer, followed by post-baking. The colored coating film thus formed may be the color filter of the present invention.

As the substrate, quartz glass, borosilicate glass, alumina silicate glass, glass plate such as soda lime glass coated with silica on the surface, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the substrate In addition, aluminum, silver, or a silver / copper / palladium alloy thin film is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

Examples of the application method include spin coating, slit coating, slit and spin coating, and the like.

The temperature for heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
When drying under reduced pressure, it is preferably performed at a temperature of 20 to 25 ° C. under a pressure of 50 to 150 Pa.
The film thickness of the colored resin composition is not particularly limited, and may be appropriately selected depending on the film thickness of the target color filter.
Furthermore, it is preferable to perform post-baking on the film | membrane of the obtained colored resin composition. The post bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-bake time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

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

The cured coating film thus obtained can be patterned by, for example, an etching method.

A colored pattern can also be produced by a photolithographic method, an inkjet method, a printing method, or the like using the colored resin composition of the present invention. Among these, when the colored resin composition contains a polymerizable compound (C) and a polymerization initiator (D), a photolithographic method is preferable. The photolithographic method is a method in which the colored resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. Application | coating and drying can be performed on the above-mentioned conditions.

The coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specific examples include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.
Use an exposure device such as a mask aligner or a stepper because the entire exposure surface can be illuminated with parallel rays uniformly, or the photomask can be accurately aligned with the substrate on which the colored composition layer is formed. Is preferred.

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

It is preferable to post-bake the resulting colored pattern. The post bake temperature and time may be the same as those described above.

According to the colored resin composition containing the colorant containing the compound of the present invention, it is possible to produce a thin color filter as compared with the case where a conventional colored resin composition is used. The color filter is useful as a color filter used for solid-state imaging devices and display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.).

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.

In the following synthesis examples, the structure of the compound was identified by mass spectrometry (LC; Agilent 1100 type, MASS; Agilent LC / MSD type) and NMR (JNM-ECA400; JEOL Ltd.).

Example 1: Compound represented by formula (I-1)

2,4-difluoroaniline (produced by Tokyo Chemical Industry Co., Ltd.) 7.00 parts, 3-bromoanisole (produced by Tokyo Chemical Industry Co., Ltd.) 10.14 parts, palladium acetate (produced by Tokyo Chemical Industry Co., Ltd.) 0 .61 parts, tertiary butylphosphine 1M hexane solution (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.86 parts, toluene (manufactured by Nacalai Tesque Co., Ltd.) 101.41 parts are put into a 300 mL four-necked flask, and 40 ° C. For 5 minutes. 7.82 parts of sodium tertiary butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was put into a four-necked flask and stirred at 110 ° C. for 10 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure. 100 parts of ethyl acetate and 100 parts of water were added and separated to obtain an ethyl acetate layer. To the ethyl acetate layer, 20 parts of ethyl acetate and 50 parts of water were added and separated to obtain an ethyl acetate layer, and the ethyl acetate was distilled off under reduced pressure. 20 parts of hexane was added to the obtained residue, and a black solid insoluble in hexane was filtered off. Sodium sulfate was added to the hexane solution for dehydration, sodium sulfate was filtered off, and hexane was distilled off under reduced pressure. The obtained residue was purified by silica gel chromatography (ethyl acetate / hexane = 1/10), and the obtained oily substance was dried under reduced pressure at 60 ° C. for 24 hours to obtain a compound represented by the formula (a-1-1). 8.16 parts were obtained (yield 64.0%).
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 236.1

3.60 parts of the compound represented by the formula (a-1-1), 4.29 parts of potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.), 12.00 parts of dimethyl sulfoxide (manufactured by Kanto Chemical Co., Ltd.) Was put into a 50 mL four-necked flask and stirred at 20 ° C. for 30 minutes. 8.87 parts of 1-bromo-2-ethylhexane (manufactured by Tokyo Chemical Industry Co., Ltd.) was put into a four-necked flask and stirred at 20 ° C. for 9 hours. While cooling with ice, 25 parts of water was added, 25 parts of ethyl acetate was added, and the mixture was separated to obtain an ethyl acetate layer. This liquid separation operation was repeated 3 times in total, and the ethyl acetate layers were combined. 25 parts of water was added to the ethyl acetate layer and the layers were separated to obtain an ethyl acetate layer. This separation operation was repeated a total of 4 times, sodium sulfate was added to the ethyl acetate layer, dehydration was performed, sodium sulfate was filtered off, and ethyl acetate was distilled off under reduced pressure. The obtained residue was purified by silica gel chromatography (toluene / hexane = 1/5), and the obtained oily substance was dried under reduced pressure at 60 ° C. for 24 hours to obtain the compound 4 represented by the formula (a-1-2). Obtained .73 parts (yield 89.0%).
(Mass Spectrometry) ionization mode ^{= ESI +: m / z =} [M + H] + 348.2

2.00 parts of the compound represented by the formula (a-1-2) and 20.00 parts of dehydrated methylene chloride (manufactured by Wako Pure Chemical Industries, Ltd.) were put into a 100 mL four-necked flask and stirred at 20 ° C. for 10 minutes. . While cooling the four-necked flask with ice, 11.88 parts of boron tribromide 17 wt% methylene chloride solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise so that the internal temperature did not exceed 10 ° C. Stir for 5 hours. In another 200 mL four-necked flask, 20 parts of methylene chloride and 25 parts of water were added, and the reaction solution was added dropwise so that the internal temperature did not exceed 10 ° C. while cooling with ice. The mixture was stirred at 20 ° C. for 2 hours, and the methylene chloride layer was separated. 40 parts of 10 wt% saline was added, and the mixture was separated to obtain an ethyl acetate layer. This separation operation was repeated a total of 4 times, sodium sulfate was added to the ethyl acetate layer, dehydration was performed, sodium sulfate was filtered off, and ethyl acetate was distilled off under reduced pressure. The obtained oily substance was dried under reduced pressure at 60 ° C. for 24 hours to obtain 1.84 parts of the compound represented by the formula (a-1-3) (yield 95.9%).
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 334.2

1.84 g of the compound represented by the formula (a-1-3), 0.31 g of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.), 1-butanol (Wako Pure) 27.00 g (manufactured by Yakuhin Co., Ltd.) and 18.00 g of toluene (manufactured by Nacalai Tesque Co., Ltd.) are charged into a 100 mL four-necked flask and removed at 115 ° C. while removing water produced using a Dean-Stark tube. Stir for hours. After completion of the reaction, the solvent was distilled off under reduced pressure, 50 parts of water was added to the resulting residue and stirred, and the water was removed by decantation. To the obtained residue, 72 parts of a mixed solvent of ethyl acetate / hexane = 1/7 was added and stirred, and the solid was filtered off and dried under reduced pressure at 60 ° C. for 24 hours to obtain a compound 0. 92 g was obtained (yield 45.7%).
(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 745.4

¹ H-NMR (400 MHz, δ value (ppm, TMS standard), CDCl ₃ ) 0.82-0.88 (m, 12H), 1.18-1.46 of the compound represented by formula (I-1) (M, 16H), 1.68 (m, 2H), 3.61 (d, 4H), 6.07 (s, 2H), 6.22 (d, 2H), 6.98 (m, 4H) 7.24 (m, 2H), 7.84 (d, 1H), 7.99 (d, 1H), 11.43 (s, 1H), 12.14 (s, 1H)

Example 2: Compound represented by formula (I-13)

Except that 2,4-difluoroaniline was changed to 10.00 parts of 2,6-difluoroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), the same operation as in Example 1 was carried out, using formula (a-13-1) 9.86 g of the indicated compound was obtained (yield 78.4%).
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 236.1

Except that the compound represented by the formula (a-1-1) was changed to 4.81 parts of the compound represented by the formula (a-13-1), the procedure of Example 1 was repeated. Thus, 5.57 g of the compound represented by 2) was obtained (yield: 85.6%).
(Mass Spectrometry) ionization mode ^{= ESI +: m / z =} [M + H] + 348.2

Except that the compound represented by the formula (a-1-2) was changed to 6.60 parts of the compound represented by the formula (a-13-2), the procedure of Example 1 was repeated. 6.31 g of the compound represented by 3) was obtained (yield 99.6%).
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 334.2

6.00 g of the compound represented by the formula (a-13-3), 1.01 g of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.), 1-butanol (Wako Pure) 90.00 g (manufactured by Yakuhin Co., Ltd.) and 60.00 g of toluene (manufactured by Nacalai Tesque Co., Ltd.) were put into a 300 mL four-necked flask, and the water produced using a Dean-Stark tube was removed at 115 ° C. Stir for hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel chromatography (chloroform / hexane = 9/4). The obtained residue was recrystallized from hexane, and the obtained solid was filtered off and dried under reduced pressure at 60 ° C. for 24 hours to obtain 1.67 g of a compound represented by the formula (I-13) (yield 25.4). %).
(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 745.4

¹ H-NMR (400 MHz, δ value (ppm, TMS standard), CDCl ₃ ) 0.81-0.87 (m, 12H), 1.21-1.47 of the compound represented by formula (I-13) (M, 16H), 1.66 (m, 2H), 3.62 (d, 4H), 6.10 (s, 2H), 6.26 (d, 2H), 7.06 (t, 4H) 7.37 (m, 2H), 7.88 (d, 1H), 8.02 (d, 1H), 11.45 (s, 1H), 12.17 (s, 1H)

Example 3: Compound represented by the formula (I-7)

Except for changing 2,4-difluoroaniline to 20.00 parts of 2,5-difluoroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), the same operation as in Example 1 was carried out, except that the formula (a-7-1) 29.84 g of the compound shown were obtained (yield 81.9%).
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 236.1

Except that the compound represented by the formula (a-1-1) is changed to 20.00 parts by weight of the compound represented by the formula (a-7-1), the same procedure as in Example 1 was carried out. 25.87 g of the compound represented by 2) was obtained (yield 98.2%).
(Mass Spectrometry) ionization mode ^{= ESI +: m / z =} [M + H] + 348.2

The compound of formula (a-7-) was prepared in the same manner as in Example 1, except that the compound represented by formula (a-1-2) was changed to 15.00 parts of the compound represented by formula (a-7-2). 13.01 g of the compound represented by 3) was obtained (yield 90.4%).
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 334.2

11.00 g of a compound represented by the formula (a-7-3), 1.84 g of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.), 1-butanol (Wako Pure) 180.00 g (manufactured by Yakuhin Co., Ltd.) and 120.00 g of toluene (manufactured by Nacalai Tesque Co., Ltd.) are charged into a 1000 mL four-necked flask and removed at 10 ° C. at 115 ° C. while removing the water produced using a Dean-Stark tube. Stir for hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the resulting residue was purified by washing with water and hexane. The obtained solid was filtered off and dried under reduced pressure at 60 ° C. for 24 hours to obtain 4.06 g of a compound represented by the formula (I-7) (yield 33.7%). (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 745.4

¹ H-NMR (400 MHz, δ value (ppm, TMS standard), CDCl ₃ ) 0.80-0.85 (m, 12H), 1.16-1.42 of the compound represented by formula (I-7) (M, 16H), 1.68-1.71 (m, 2H), 3.63 (d, 4H), 6.09 (s, 2H), 6.24 (d, 2H), 6.99 ( m, 2H), 7.05 (m, 2H), 7.17 (m, 2H), 7.84 (d, 1H), 7.99 (d, 1H), 11.43 (s, 1H), 12.15 (s, 1H)

Example 4: Compound represented by formula (I-19)

Except that 2,4-difluoroaniline was changed to 25.00 parts of 2-aminobenzotrifluoride (manufactured by Tokyo Chemical Industry Co., Ltd.), the same operation as in Example 1 was carried out, except that formula (a-19-1) 14.33 g of the compound shown were obtained (yield 23.8%).
(Mass Spectrometry) ionization mode ^{= ESI +: m / z =} [M + H] + 268.1

The compound of formula (a-19-) was prepared in the same manner as in Example 1, except that the compound represented by formula (a-1-1) was changed to 7.00 parts of compound represented by formula (a-19-1). Thus, 3.71 g of the compound represented by 2) was obtained (yield 62.8%).
(Mass Spectrometry) ionization mode ^{= ESI +: m / z =} [M + H] + 380.2

The compound of formula (a-19-) was prepared in the same manner as in Example 1, except that the compound represented by formula (a-1-2) was changed to 3.71 parts of the compound represented by formula (a-19-2). 2.32 g of the compound represented by 3) was obtained (yield 64.9%).
(Mass Spectrometry) ionization mode ^{= ESI +: m / z =} [M + H] + 366.2

2.30 g of the compound represented by the formula (a-19-3), 0.35 g of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.), 1-butanol (Wako Pure) Yakuhin Co., Ltd. (33.00 g) and toluene (Nacalai Tesque Co., Ltd.) 22.00 g were put into a 200 mL four-necked flask, and the water generated using a Dean-Stark tube was removed at 115 ° C. while removing water. Stir for hours. After completion of the reaction, the solvent was distilled off under reduced pressure, 30 parts of water was added to the resulting residue and stirred, and water was decanted off. The obtained residue was purified by silica gel chromatography (chloroform / hexane = 1/1). The mixture was dried under reduced pressure at 60 ° C. for 24 hours to obtain 0.80 g of the compound represented by the formula (I-19) (yield 32.1%).
(Mass Spectrometry) ionization mode ^{= ESI +: m / z =} [M + H] + 809.4

¹ H-NMR (400 MHz, δ value (ppm, TMS standard), CDCl ₃ ) 0.72-0.92 (m, 12H), 1.17-1.44 of the compound represented by formula (I-19) (M, 16H), 1.77 (m, 2H), 3.27 (m, 2H), 3.90 (m, 2H), 5.92 (s, 2H), 6.09 (s, 2H) , 7.31 (t, 2H), 7.54 (t, 2H), 7.67 (t, 2H), 7.80 (t, 4H), 11.38 (s, 1H), 12.10 ( s, 1H)

Comparative Example 1: Compound Represented by Formula (I′-1) A compound represented by the following formula (I′-1) was produced by the method described in JP-A-2015-86379.

0.35 g of the compound represented by formula (I-1) is dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which is diluted with chloroform to a volume of 100 cm ³ (concentration: 0.028 g / L) The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound had λmax = 639 nm.

The absorption spectrum of the compound represented by formula (I-13) was measured by the same method. This compound had λmax = 636 nm.

In the same manner, the absorption spectrum of the compound represented by the formula (I-7) was measured. This compound had λmax = 640 nm.

In the same manner, the absorption spectrum of the compound represented by the formula (I-19) was measured. This compound had λmax = 638 nm.

In the same manner, the absorption spectrum of the compound represented by the formula (I′-1) was measured. This compound had λmax = 649 nm.

Table 2 shows the absorption spectra measured for the compounds represented by formulas (I-1), (I-13), (I-7), (I-19) and (I′-1) at 640 nm near λmax. Absorbance is shown.

[Synthesis of Resin B-1]
An appropriate amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer to make a nitrogen atmosphere, 290 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85 ° C. with stirring. Then, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9 A mixed solution of 94 parts of a mixture of -yl acrylate (content ratio of 1: 1), 61 parts of 4-vinylbenzoic acid, 157 parts of phenyl methacrylate, and 250 parts of propylene glycol monomethyl ether acetate was added dropwise over 4 hours. On the other hand, a mixed solution prepared by dissolving 9 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 110 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of dropping, the flask was kept at 85 ° C. for 3 hours and then cooled to room temperature to obtain a copolymer (resin B-1) solution having a B-type viscosity (23 ° C.) of 70 mPas and a solid content of 28.2%. It was. The produced copolymer had a weight average molecular weight Mw of 17000 and a degree of dispersion of 2.23. Resin B-1 thus obtained has the structural units shown below.

[Preparation of colored resin composition]
Examples 5 and 6 and Comparative Example 2
Each component was mixed so that it might become a composition shown in following Table 3, and the colored resin composition was obtained.

Each component in Table 3 is shown below.
Dye: I-13: Dye represented by formula (I-13) I-19: Dye represented by formula (I-19) I′-1: Dye represented by formula (I′-1) I '' -1: a dye represented by the following formula produced by the method described in JP-A-2016-11419

Resin: Resin B-1 synthesized above (in terms of solid content)
Leveling agent: Megafac (registered trademark) F554 (manufactured by DIC Corporation)
Solvent: PGMEA (propylene glycol monomethyl ether acetate)

[Formation of coating film]
A colored resin prepared in Examples 5 and 6 and Comparative Example 2 by spin coating so that the film thickness after post-baking is 0.5 μm on a 5 cm square glass substrate (Eagle XG; manufactured by Corning). After each composition was applied, it was pre-baked on a hot plate at 70 ° C. for 1 minute. Then, the colored coating film was obtained by performing post-baking for 3 minutes at 220 degreeC on a hotplate.

<Chromaticity evaluation>
About the obtained colored coating film, the spectrum was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity in the XYZ color system of CIE was measured using the characteristic function of the C light source. The coordinates (x, y) and the tristimulus value Y were measured.
The results are shown in Table 4.

As shown in Table 4, in Examples 5 and 6 using the compound of the present invention, the same chromaticity value was obtained even when the dye content was small as compared with Comparative Example 2. As shown in Table 2, the compounds represented by the formulas (I-1), (I-13), (I-7) and (I-19) of Examples 1 to 4 are represented by the formula ( It can be seen that the absorbance at 640 nm is higher than that of the compound represented by I′-1). For this reason, the compounds represented by formulas (I-1) and (I-7) also have the same color in the colored resin composition as the compounds represented by formulas (I-13) and (I-19). It is understood that the colorant content can be reduced when achieving the degree value, compared to conventional colorants.

Claims

A compound represented by formula (I).

[In the formula (I),
R 1 to R 4 each independently represents a hydrogen atom, a halogen atom, a hydroxy group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is a halogen atom , A hydroxy group or —N (R a ) 2 may be substituted, and —CH 2 — contained in the saturated hydrocarbon group may be replaced with —O— or —S—. R a represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R 5 to R 8 each independently represents a hydrogen atom or a hydroxy group.
R 9 and R 10 each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group includes a halogen atom, a hydroxy group, —N (R b ) 2 or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, and —CH 2 — contained in the saturated hydrocarbon group is —O—, — S—, —NR b — or —C (═O) — may be substituted. R b represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R 11 and R 12 each independently represents a halogen atom or a halogenated alkyl group having 1 to 6 carbon atoms.
m1 and m2 each independently represents an integer of 1 to 5. When m1 is 2 or more, the plurality of R 11 may be the same or different, and when m2 is 2 or more, the plurality of R 12 may be the same or different. ]
A colored resin composition comprising a colorant comprising the compound according to claim 1 and a resin.
A color filter formed from the colored resin composition according to claim 2.
A solid-state imaging device including the color filter according to claim 3.
It is a manufacturing method of the compound of Claim 1, Comprising:
A compound represented by the following formula (IV-1) is reacted with 3,4-dihydroxy-3-cyclobutene-1,2-dione, or a compound represented by the following formula (IV-1) and 3, 4-dihydroxy-3-cyclobutene-1,2-dione is reacted, and the resulting compound represented by the following formula (V-1) and the compound represented by the following formula (IV-2) are reacted. ,Production method.

[In formula (IV-1), formula (V-1), and formula (IV-2),
R 1 to R 4 each independently represents a hydrogen atom, a halogen atom, a hydroxy group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is a halogen atom , A hydroxy group or —N (R a ) 2 may be substituted, and —CH 2 — contained in the saturated hydrocarbon group may be replaced with —O— or —S—. R a represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R 5 to R 8 each independently represents a hydrogen atom or a hydroxy group.
R 9 and R 10 each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group includes a halogen atom, a hydroxy group, —N (R b ) 2 or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, and —CH 2 — contained in the saturated hydrocarbon group is —O—, — S—, —NR b — or —C (═O) — may be substituted. R b represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R 11 and R 12 each independently represents a halogen atom or a halogenated alkyl group having 1 to 6 carbon atoms.
m1 and m2 each independently represents an integer of 1 to 5. When m1 is 2 or more, the plurality of R 11 may be the same or different, and when m2 is 2 or more, the plurality of R 12 may be the same or different.
A compound represented by the formula (IV-1) according to claim 5.