TW201736523A - Method for preparing dye solution, colored curable resin composition comprising the dye solution, color filter and display device mixing a xanthene dye and at least one member selected from the group consisting of a salt of an organic acid and a silicon atom-containing compound in the presence of an organic solvent - Google Patents

Abstract

This invention provides a method for producing a xanthene dye solution having excellent temporal stability, a colored curable resin composition comprising the dye solution, a color filter and a display device. The method for producing a dye solution according to the present invention is characterized by comprising the steps of: (a) mixing a xanthene dye and (b) at least one member selected from the group consisting of a salt of an organic acid and a silicon atom-containing compound in the presence of an organic solvent.

Description

Method for producing dye solution, color-curable resin composition containing the above dye solution, color filter, and display device

Field of invention

The present invention relates to a method of producing a dye solution.

Background of the invention

For example, in the field of fiber materials, liquid crystal display devices, inkjet, and the like, in order to perform color display using reflected light or transmitted light, a dye is used. As such a dye, for example, rhodamine B having a xanthene skeleton and represented by the following formula (Rb) is known (Non-Patent Document 1).

Prior art literature

Non-patent literature

Non-Patent Document 1: Hiroshi Hiroshi, "New Dye Chemistry", Co., Ltd., 1st Edition, May 1973, p. 274

Summary of invention

When a xanthene dye is used for the above-mentioned use, the xanthene dye is usually used in the form of a solution dissolved in an organic solvent from the viewpoint of uniform coloring. However, it is difficult to dissolve the xanthene dye itself in an organic solvent, and if a solution containing a xanthene dye is stored in such a state, it is known that precipitates are generated due to changes over time even after about one week. A dye solution containing precipitates cannot be used for the above purposes, which is a problem.

Under such circumstances, the present invention has been made as a subject of the invention to provide a method for producing a xanthene dye solution which is excellent in stability over time.

The present invention has the following points in the following aspects.

[1] A method for producing a dye-dissolving solution, comprising: at least one selected from the group consisting of (a) a xanthene dye, and (b) a salt selected from an organic acid and a germanium atom-containing compound in the presence of an organic solvent; The process of stirring.

[2] The method for producing a dye solution according to [1], further comprising a solid-liquid separation step after the stirring step.

The method for producing a dye solution according to the above aspect, wherein the organic acid is selected from the group consisting of aliphatic carboxylic acids, aromatic carboxylic acids, aliphatic sulfonic acids, alicyclic sulfonic acids, and aromatics. At least one of a compound represented by the following formula (h1) and a compound represented by the following formula (h2), the aliphatic carboxylic acid, the aromatic carboxylic acid, and the above aliphatic sulfonic acid The hydrogen atom other than the acidic proton of the aromatic sulfonic acid may be substituted by a halogen atom or a hydroxyl group, and the above-mentioned aliphatic carboxylic acid, aliphatic sulfonic acid, and -CH ₂ - of the above alicyclic sulfonic acid may be - CO-replacement.

[In the formula (h1), X ^h1 and X ^h2 independently of each other represent a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms, or X ^h1 and X ^{h2 are} combined to form a fluoroalkylene group having 2 to 4 carbon atoms; base.

In the formula (h2), X ^h3 to X ^h5 independently represent a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms. ]

The method for producing a dye-dissolving solution according to any one of the above aspects, wherein the compound containing a ruthenium atom is a compound represented by the following formula (j).

[Chemical Formula 3] R ^h2 -Si-(R ^h1 ) ₃ (j)

In the formula (j), R ^h1 represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and a plurality of ^Rh1 may be the same or different, and ^{Rh 2} represents a monovalent value. Substituents. ]

The method for producing a dye-dissolving solution according to any one of the aspects of the present invention, wherein the organic solvent is a carboxylic acid ester of an alkylene glycol monoalkyl ether or a ketone carbonyl group. An aliphatic alcohol or a mixed solvent thereof.

[6] The manufacturer of the dye solution according to any one of [1] to [5] The method wherein the xanthene dye is represented by the following formula (1a).

In the formula (1a), R ¹ to R ⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a monovalent carbon number of 6 to 10 which may have a substituent. An aromatic hydrocarbon group or a group represented by the formula (ii).

*-R ⁵⁰ -Si(R ²⁹ ) ₃ (ii)

(In the formula (ii), R ²⁹ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and a plurality of R ^{29 's} may be the same or different.

R ⁵⁰ represents an alkylene group having 1 to 10 carbon atoms, and -CH ₂ - constituting the alkylene group may be -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO- replacement. However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

Indicates the bonding end with a nitrogen atom. )

In R ¹ to R ⁴ , -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -NHCOO-, - In the case of CONH- or -NHCO-, R ¹ and R ² may together form a ring containing a nitrogen atom, and R ³ and R ⁴ may together form a ring containing a nitrogen atom. However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

R ⁵ represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ .

R ⁶ and R ⁷ independently of each other represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

m represents an integer from 0 to 5. When m is 2 or more, a plurality of R ^{5 's} may be the same or different.

a represents an integer of 0 or 1.

X represents a halogen atom.

Z ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and four R ^{11 's} may be the same or different.

R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom.

R ⁹ and R ¹⁰ independently of each other represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-, R ⁹ and R ¹⁰ may be bonded to each other to form a 3 to 10 membered ring containing a nitrogen atom. Heterocyclic. However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. ]

[7] The method for producing a dye solution according to any one of [1] to [6] In the above method, the xanthene dye is a compound represented by the following formula (1d).

In the formula (1d), R ^1d to R ^4d independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a monovalent carbon having 6 to 10 carbon atoms which may have a substituent. The aromatic hydrocarbon group or the group represented by the formula (ii), at least one of R ^1d to R ^4d is a group represented by the formula (ii).

*-R ⁵⁰ -Si(R ²⁹ ) ₃ (ii)

(In the formula (ii), R ²⁹ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and a plurality of R ^{29 's} may be the same or different.

R ⁵⁰ represents an alkylene group having 1 to 10 carbon atoms, and -CH ₂ - constituting the alkylene group may be -O-, -CO-, -NR ^11d -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO- replacement. However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

Indicates the bonding end with a nitrogen atom. )

In R ^1d to R ^4d , -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO-, -NR ^11d -, -OCO-, -COO-, -OCONH-, -NHCOO-, - In the case of CONH- or -NHCO-, R ^1d and R ^2d may together form a ring containing a nitrogen atom, and R ^3d and R ^4d may together form a ring containing a nitrogen atom. However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

R ^5d represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Zd ⁺ , -CO ₂ H, -CO ₂ ^- Zd ⁺ , -CO ₂ R ^8d , -SO ₃ R ^8d or -SO ₂ NR ^9d R ^10d .

R ^6d and R ^7d independently of each other represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Md represents an integer from 0 to 5. When md is 2 or more, a plurality of R ^5d may be the same or different.

d represents an integer of 0 or 1.

Xd represents a halogen atom.

Zd ⁺ represents ⁺ N(R ^11d ) ₄ , Na ⁺ or K ⁺ , and the four R ^11d may be the same or different.

R ^8d represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom.

R ^9d and R ^10d independently of each other represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO-, -NR ^11d -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-, R ^9d and R ^10d may be bonded to each other to form a 3 to 10 membered ring containing a nitrogen atom. Heterocyclic. However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

R ^11d represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. ]

[8] The dye-soluble resin composition according to any one of [1] to [7], the resin (B), the polymerizable compound (C), and a polymerization initiator (D).

[9] A color filter formed from the colored curable resin composition according to [8].

[10] A display device comprising the color filter according to [9].

According to the method for producing a dye-dissolving liquid according to the present invention, in the obtained dye solution, foreign matter can be suppressed from being changed with time, and therefore it is stable over time. Therefore, the dye solution to be produced can be applied to a wide range of applications such as dyes for coloring curable compositions.

detailed description

A method for producing a dye-dissolving solution according to the present invention, comprising: at least 1 of (a) xanthene dye, and (b) a salt selected from an organic acid and a halogen atom-containing compound in the presence of an organic solvent; A process of stirring.

By stirring the xanthene dye (a) and (b) which is at least one selected from the group consisting of a salt selected from an organic acid and a compound containing a ruthenium atom, the xanthene dye (a) cannot be used alone. The effect of stability over time.

<Method for Producing Dye Dissolving Solution>

The dye solution obtained in the present invention contains at least one of (a) xanthene dye, (b) a salt selected from an organic acid, and a compound containing a halogen atom, and an organic solvent. Further, the dye solution is obtained by stirring at least one of (a) xanthene dye, and (b) a salt selected from an organic acid and a halogen atom-containing compound in the presence of an organic solvent.

<呫吨染料(a)>

The xanthene dye (a) used in the present invention is a dye containing a compound having a xanthene skeleton in the molecule, and the xanthene dye (a) preferably contains a compound represented by the formula (1a) (hereinafter sometimes referred to as " Dye of compound (1a)".). Compound (1a) may be a tautomer thereof.

In the formula (1a), R ¹ to R ⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a monovalent carbon number of 6 to 10 which may have a substituent. An aromatic hydrocarbon group or a group represented by the formula (ii).

*-R ⁵⁰ -Si(R ²⁹ ) ₃ (ii)

(R ²⁹ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and a plurality of R ^{29 's} may be the same or different.

R ⁵⁰ represents an alkylene group having 1 to 10 carbon atoms, and -CH ₂ - constituting the alkylene group may be -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO- replacement. However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

* indicates the bonding end with a nitrogen atom. )

In R ¹ to R ⁴ , -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -NHCOO-, - In place of CONH- or -NHCO-, R ¹ and R ² may together form a ring containing a nitrogen atom, and R ³ and R ⁴ may together form a ring containing a nitrogen atom. However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

R ⁵ represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ .

R ⁶ and R ⁷ independently of each other represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

m represents an integer from 0 to 5. When m is 2 or more, a plurality of R ^{5 's} may be the same or different.

a represents an integer of 0 or 1.

X represents a halogen atom.

Z ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and four R ^{11 's} may be the same or different.

R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom.

R ⁹ and R ¹⁰ independently of each other represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-, R ⁹ and R ¹⁰ may be bonded to each other to form a 3 to 10 membered ring containing a nitrogen atom. Heterocyclic. However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. ]

In the formula (1a), in the case where -SO ₃ ^{- is} present, the number thereof is one.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group. .

The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms may have a substituent. Examples of the substituent which the aromatic hydrocarbon group may have include a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ , preferably these substituents are substituted with a hydrogen atom contained in the aromatic hydrocarbon group. Among these, as the substituent, -R ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ are preferable, and -R ⁸ , -SO ₃ ^- Z ⁺ and more are more preferable. -SO ₂ NR ⁹ R ¹⁰ . As the -R ^{8 in} this case, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is more preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable. Further, as -SO ₃ ^- Z ^{+ in} this case, -SO ₃ ^-+ N(R ¹¹ ) ₄ is preferable.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ¹ to R ⁴ and R ⁸ to R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. a linear alkyl group such as octyl, decyl, decyl, dodecyl, hexadecyl or eicosyl; isopropyl, isobutyl, isopentyl, neopentyl, 2-ethyl a branched chain alkyl group such as a hexyl group; an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a tricyclodecyl group.

-CH ₂ - contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO- . However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

The group in which -CH ₂ - contained in the saturated hydrocarbon group is replaced by -O- includes, for example, the following groups (* represents a bonding end).

The group in which -CH ₂ - contained in the saturated hydrocarbon group is replaced by -CO- includes, for example, the following groups (* represents a bonding end).

The group in which -CH ₂ - contained in the saturated hydrocarbon group is replaced by -NR ¹¹ - may, for example, be the following group (* represents a bonding end).

[Chemical Formula 9]

The group in which -CH ₂ - contained in the saturated hydrocarbon group is replaced by -OCO- includes, for example, the following groups (* represents a bonding end).

The group in which -CH ₂ - contained in the saturated hydrocarbon group is replaced by -COO- includes, for example, the following groups (* represents a bonding end).

The group in which -CH ₂ - contained in the saturated hydrocarbon group is replaced by -OCONH- includes, for example, the following groups (* represents a bonding end).

The group in which -CH ₂ - contained in the saturated hydrocarbon group is replaced by -NHCOO- includes, for example, the following groups (* represents a bonding end).

[Chemical Formula 13]

The group in which -CH ₂ - contained in the saturated hydrocarbon group is replaced by -CONH- includes, for example, the following groups (* represents a bonding end).

The group in which -CH ₂ - contained in the saturated hydrocarbon group is replaced by -NHCO- includes, for example, the following groups (* represents a bonding end).

The hydrogen atom contained in the saturated hydrocarbon group in R ¹ to R ⁴ may be substituted with, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom as a substituent. The aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with a hydrogen atom of a saturated hydrocarbon group of R ¹ to R ⁴ may be exemplified as the aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ . The same group of the group.

The hydrogen atom contained in the saturated hydrocarbon group in R ⁹ and R ¹⁰ may be substituted, for example, by a hydroxyl group or a halogen atom as a substituent.

Examples of the ring formed by R ¹ and R ² together with the ring formed by R ³ and R ⁴ include the following rings.

Examples of -OR ⁸ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group and two. An alkoxy group such as a decadecyloxy group.

Examples of the -CO ₂ R ⁸ include alkoxycarbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an eicosyloxycarbonyl group.

Examples of -SR ⁸ include alkylsulfane groups such as methylsulfanyl group, ethylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, mercaptosulfanyl group, and eicosylsulfanyl group. Base.

Examples of the -SO ₂ R ⁸ include an alkyl group such as a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a nonylsulfonyl group, and an eicosylsulfonyl group. Sulfonyl and the like.

Examples of -SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an eicosane. An alkoxysulfonyl group such as oxysulfonyl group.

Examples of -SO ₂ NR ⁹ R ¹⁰ include an aminesulfonyl group; N-methylaminesulfonyl group, N-ethylaminesulfonyl group, N-propylaminesulfonyl group, and N-isopropyl group; Aminesulfonyl, N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-sec-butylamine sulfonyl, N-tert-butylamine sulfonyl, N-pentylamine sulfonate Sulfhydryl, N-(1-ethylpropyl)amine sulfonyl, N-(1,1-dimethylpropyl)amine sulfonyl, N-(1,2-dimethylpropyl)amine Sulfonyl, N-(2,2-dimethylpropyl)aminesulfonyl, N-(1-methylbutyl)aminesulfonyl, N-(2-methylbutyl)aminesulfonate , N-(3-methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, N-hexylamine sulfonyl, N-(1,3-dimethylbutyl)amine sulfonate Indenyl, N-(3,3-dimethylbutyl)aminesulfonyl, N-heptylaminesulfonyl, N-(1-methylhexyl)aminesulfonyl, N-(1,4 -Dimethylpentyl)aminesulfonyl, N-octylaminesulfonyl, N-(2-ethylhexyl)aminesulfonyl, N-(1,5-dimethylhexyl)aminesulfonate N-substituted sulfonyl group such as N-(1,1,2,2-tetramethylbutyl)amine sulfonyl group; N,N-dimethylamine sulfonyl group, N,N-B Methylamine sulfonyl, N,N-diethylamine sulfonyl, N,N-propyl Amidoxime, N,N-isopropylmethylaminesulfonyl, N,N-tert-butylmethylaminesulfonyl, N,N-butylethylaminesulfonyl, N,N-double An N,N-2 substituted amine sulfonyl group such as (1-methylpropyl)amine sulfonyl group and N,N-heptylmethylamine sulfonyl group.

As R ⁵ , preferably -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H and -SO ₂ NHR ⁹ , more preferably -SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H and -SO ₂ NHR ⁹ .

m is preferably from 1 to 4, more preferably from 1 or 2.

As the compound (1a), a phenyl group substituted with a (R ⁵ ) _m group in the formula (1a) is preferably a compound of any one of the formulae (R ⁵ -1) to (R ⁵ -37), and more preferably a formula (1). The compound of any one of R ⁵ -1) to the formula (R ⁵ -25) is more preferably a compound of any one of the formulae (R ⁵ -1) to (R ⁵ -5), and particularly preferably a formula (R ^{5 )} -1) compound. Further, in the formula (R ⁵ -1) to the formula (R ⁵ -37), R ⁴⁰ and R ⁴¹ each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branch having 6 to 12 carbon atoms. A chain alkyl group is more preferably 2-ethylhexyl.

Examples of the alkyl group having 1 to 6 carbon atoms in R ⁶ and R ⁷ include a group having 1 to 6 carbon atoms in the above-exemplified alkyl group.

As R ⁶ and R ⁷ , a hydrogen atom is preferred.

R ⁹ and R ¹⁰ may together with a nitrogen atom represent a 3 to 10 membered nitrogen-containing heterocyclic ring. Examples of the hetero ring include the following nitrogen-containing heterocyclic rings.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ¹¹ include a benzyl group, a phenylethyl group, and a phenylbutyl group.

Z ⁺ is ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ¹¹ ) ₄ .

As the above ⁺ N(R ¹¹ ) ₄ , at least two of the four R ¹¹ are preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ¹¹ is preferably 20 to 80, and more preferably 20 to 60. When ⁺ N(R ¹¹ ) ₄ is present in the compound (1a), when R ¹¹ is such a group, the colored curable resin composition of the present invention containing the compound (1a) can form a color filter having less foreign matter. Device.

X is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

a is 0 or 1, preferably 0.

Further, R ¹ to R ⁴ may represent a group represented by the following formula (ii).

*-R ⁵⁰ -Si(R ²⁹ ) ₃ (ii)

(R ²⁹ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and a plurality of R ^{29 's} may be the same or different.

R ⁵⁰ represents an alkylene group having 1 to 10 carbon atoms, and -CH ₂ - constituting the alkylene group may be -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO- substituted. However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

* indicates the bonding end with a nitrogen atom. )

R ²⁹ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and a plurality of R ^{29 's} may be the same or different.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ²⁹ include a methyl group, an ethyl group, a propyl group and a butyl group.

Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ²⁹ include a methoxy group, an ethoxy group, a propoxy group, and a t-butoxy group.

R ²⁹ is preferably a hydroxyl group and an alkoxy group having 1 to 4 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, still more preferably a methyl group, an ethyl group, a methoxy group or an ethoxy group, and particularly preferably a methoxy group. And ethoxylated.

Examples of the alkylene group having 1 to 10 carbon atoms represented by R ⁵⁰ include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and an isopropylidene group. , isobutylene, 2-methyltrimethylene, isoisopentyl, isohexylene, isoisooctyl and 2-ethylhexylene, etc., among which, preferably, the carbon number is 1 to 6. The alkylene group is more preferably an alkylene group having 1 to 4 carbon atoms.

-CH ₂ - constituting the alkylene group represented by R ⁵⁰ may be -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-replacement. However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

The group represented by the formula (ii) is, for example, a group represented by the following formulas (ii-1) to (ii-24).

In the formula (ii), the group in which -CH ₂ - which is a member of R ⁵⁰ is replaced by -O- includes, for example, a group shown below (* represents a bonding end).

In the formula (ii), the group in which -CH ₂ - constituting R ⁵⁰ is replaced by -CO- includes, for example, a group shown below (* represents a bonding end).

In the formula (ii), the group in which -CH ₂ - constituting R ⁵⁰ is replaced by -NR ¹¹ - may, for example, be a group shown below (* represents a bonding end).

In the formula (ii), the group in which -CH ₂ - constituting R ⁵⁰ is replaced by -OCO- includes, for example, a group shown below (* represents a bonding end).

In the formula (ii), examples of the group in which -CH ₂ - constituting R ⁵⁰ is replaced by -COO- include the following groups (* indicates a bonding end).

In the formula (ii), the group in which -CH ₂ - constituting R ⁵⁰ is replaced by -OCONH- includes, for example, a group shown below (* represents a bonding end).

In the formula (ii), the group in which -CH ₂ - constituting R ⁵⁰ is replaced by -NHCOO- includes, for example, a group shown below (* represents a bonding end).

In the formula (ii), the group in which -CH ₂ - constituting R ⁵⁰ is replaced by -CONH- includes, for example, the group shown below (* represents a bonding end).

In the formula (ii), the group in which -CH ₂ - constituting R ⁵⁰ is replaced by -NHCO- includes, for example, a group shown below (* represents a bonding end).

When the compound (1a) has a substituent represented by the formula (ii), the substituent of the formula (ii), preferably R ²⁹ is a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms, more preferably R ²⁹ is a hydroxyl group or The substituent having an alkoxy group having 1 to 4 carbon atoms and an alkylene group having R ⁵⁰ of 1 to 10 carbon atoms is more preferably a substituent represented by the following formula (i).

(In the formula (i), n represents an integer of 1 to 8, and R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the plurality of OR ¹² may be the same or different.

* indicates the bonding end with a nitrogen atom. )

n is preferably from 1 to 6, more preferably from 1 to 5, still more preferably from 1 to 4.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹² include a methyl group, an ethyl group, a propyl group, and a butyl group.

R ¹² is preferably a hydrogen atom, a methyl group, an ethyl group or a propyl group, and more preferably a hydrogen atom, a methyl group or an ethyl group.

The group represented by the formula (i) is, for example, a group represented by the following formulas (i-1) to (i-12). The group represented by the formula (i) is preferably a group represented by the formula (i-2), a group represented by the formula (i-3), a group represented by the formula (i-5), or a formula. The group represented by (i-6) is more preferably a group represented by the formula (i-3).

The compound represented by the formula (1a) can be classified into a substituent having no substituent represented by the formula (ii) by the following formula (1a-) depending on the presence or absence of the group represented by the formula (ii) in R ¹ to R ⁴ . 1) A compound represented by the following formula (1a-2) and a compound having a substituent represented by the formula (ii). The more preferable compounds among the compounds represented by the following formula (1a-1) and the compounds represented by the following formula (1a-2) will be described in detail below.

In the above formula (1a), R ¹ to R ⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon number which may have a substituent a monovalent aromatic hydrocarbon group of 6 to 10, and in R ¹ to R ⁴ , -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO-, -NR ¹¹ -, -OCO-, -COO -, -OCONH-, -NHCOO-, -CONH- or -NHCO-, R ¹ and R ² may together form a ring containing a nitrogen atom, and R ³ and R ⁴ may together form a ring containing a nitrogen atom, R ⁵ ~ R ¹¹ , m, a, X, Z ⁺ are the same compounds as above. In the above formula (1a), R ¹ to R ⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a carbon number which may have a substituent 6 to 10 of a monovalent aromatic hydrocarbon group or a group represented by the formula (ii), and at least one of R ¹ to R ⁴ is a group represented by the formula (ii). In R ¹ to R ⁴ , -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -NHCOO-, - CONH- or -NHCO-substitution, R ¹ and R ² may together form a ring containing a nitrogen atom, and R ³ and R ⁴ may together form a ring containing a nitrogen atom, R ⁵ to R ¹¹ , R ²⁹ , R ⁵⁰ , m, a, X, Z ⁺ the same compound as above.

The compound represented by the formula (1a-1) is preferably a compound represented by the following formula (1b) (hereinafter sometimes referred to as "compound (1b)"). Compound (1b) may be a tautomer thereof.

In the formula (1b), R ^1b to R ^4b each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ contained in the saturated hydrocarbon group in R ^1b to R ^4b - may be replaced by -O-, -CO-, -NR ^11b -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-, and R ^1b and R ^2b may together form The ring of the nitrogen atom, R ^3b and R ^{4b ,} together may form a ring containing a nitrogen atom. However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

R ^5b represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Zb ⁺ , -CO ₂ H, -CO ₂ ^- Zb ⁺ , -CO ₂ R ^8b , -SO ₃ R ^8b or -SO ₂ NR ^9b R ^10b .

R ^6b and R ^7b independently of each other represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Mb represents an integer from 0 to 5. When mb is 2 or more, a plurality of R ^5b may be the same or different.

b represents an integer of 0 or 1.

Xb represents a halogen atom.

Zb ⁺ represents ⁺ N(R ^11b ) ₄ , Na ⁺ or K ⁺ , and the four R ^11b may be the same or different.

R ^8b represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom.

R ^9b and R ^10b independently of each other represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO-, -NR ^11b -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-, R ^9b and R ^10b may be bonded to each other to form a 3 to 10 membered ring containing a nitrogen atom. Heterocyclic. However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

R ^11b represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. ]

In the formula (1b), in the case where -SO ₃ ^{- is} present, the number is one.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ^1b to R ^4b and R ^8b to R ^11b include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Linear alkyl groups such as octyl, decyl, decyl, dodecyl, hexadecyl and eicosyl; isopropyl, isobutyl, isopentyl, neopentyl and 2-ethyl a branched chain alkyl group such as a hexyl group; an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group.

-CH ₂ - contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, -NR ^11b -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO- . However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

The hydrogen atom contained in the saturated hydrocarbon group in R ^1b to R ^4b may be substituted with, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom as a substituent. The aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with a hydrogen atom of a saturated hydrocarbon group of R ^1b to R ^4b may be exemplified as the aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ . The same group of the group.

The hydrogen atom contained in the saturated hydrocarbon group in R ^9b and R ^10b may be substituted with, for example, a hydroxyl group or a halogen atom as a substituent.

Compound (1b), preferably, R ^4b ~ R ^1b and R ^1b in R ^2b, R ^3b and R ^4b are the same as the saturated hydrocarbon, e.g., preferably R ^1b and R ^2b, R ^3b and R ^4b are linear The combination of alkyl groups is more preferably a combination of R ^1b and R ^2b , and R ^3b and R ^4b are each a linear alkyl group having 1 to 5 carbon atoms, and more preferably R ^1b and R ^2b , and R ^3b and R ^4b respectively. It is a combination of two types selected from a methyl group, an ethyl group, a propyl group, and a butyl group.

Examples of the ring formed by R ^1b and R ^2b together with the ring formed by R ^3b and R ^4b include the following rings.

Examples of -OR ^8b include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group and two. An alkoxy group such as a decadecyloxy group.

Examples of the -CO ₂ R ^8b include alkoxycarbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group and an eicosyloxycarbonyl group.

Examples of the -SR ^8b include alkylsulfane groups such as methylsulfanyl group, ethylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, mercaptosulfanyl group, and eicosylsulfanyl group. Base.

Examples of the -SO ₂ R ^8b include an alkyl group such as a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a nonylsulfonyl group, and an eicosylsulfonyl group. Sulfonyl and the like.

Examples of -SO ₃ R ^8b include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an eicosane. An alkoxysulfonyl group such as oxysulfonyl group.

Examples of -SO ₂ NR ^9b R ^10b include an aminesulfonyl group; N-methylaminesulfonyl group, N-ethylaminesulfonyl group, N-propylaminesulfonyl group, and N-isopropyl group; Amine sulfonyl, N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-sec-butylamine sulfonyl, N-tert-butylamine sulfonyl, N-pentylamine Sulfonyl, N-(1-ethylpropyl)aminesulfonyl, N-(1,1-dimethylpropyl)aminesulfonyl, N-(1,2-dimethylpropyl) Aminesulfonyl, N-(2,2-dimethylpropyl)aminesulfonyl, N-(1-methylbutyl)aminesulfonyl, N-(2-methylbutyl)aminesulfonate Mercapto, N-(3-methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, N-hexylamine sulfonyl, N-(1,3-dimethylbutyl)amine Sulfosyl, N-(3,3-dimethylbutyl)amine sulfonyl, N-heptylamine sulfonyl, N-(1-methylhexyl)amine sulfonyl, N-(1, 4-dimethylpentyl)amine sulfonyl, N-octylamine sulfonyl, N-(2-ethylhexyl)amine sulfonyl, N-(1,5-dimethylhexyl)amine sulfonate N-1 substituted amine sulfonyl group such as fluorenyl, N-(1,1,2,2-tetramethylbutyl)amine sulfonyl group; N,N-dimethylamine sulfonyl group, N,N- Ethylmethylamine sulfonyl, N,N-diethylamine sulfonyl, N,N- Methylamine sulfonyl, N,N-isopropylmethylamine sulfonyl, N,N-tert-butylmethylamine sulfonyl, N,N-butylethylamine sulfonyl, N,N An N,N-2 substituted amine sulfonyl group such as bis(1-methylpropyl)amine sulfonyl group or N,N-heptylmethylamine sulfonyl group.

As R ^5b , preferably -CO ₂ H, -CO ₂ ^- Zb ⁺ , -CO ₂ R ^8b , -SO ₃ ^- , -SO ₃ ^- Zb ⁺ , -SO ₃ H or -SO ₂ NHR ^9b , more preferably -SO ₃ ^- , -SO ₃ ^- Zb ⁺ , -SO ₃ H or -SO ₂ NHR ^9b .

Mb is preferably 1 to 4, more preferably 1 or 2.

In the compound (1b), the phenyl group substituted with the (R ^5b ) _mb group is preferably any one of the above (R ⁵ -1) to (R ⁵ -37), and more preferably (R ⁵ -1) to (R). Any one of ^{5 to} 25) is more preferably (R ⁵ -1) to (R ⁵ -5), and particularly preferably (R ⁵ -1).

Examples of the alkyl group having 1 to 6 carbon atoms in R ^6b and R ^7b include an alkyl group having 1 to 6 carbon atoms in the above-exemplified alkyl group. Among them, as R ^6b and R ^7b , a hydrogen atom is preferred.

R ^9b and R ^10b may together with a nitrogen atom represent a 3 to 10 membered nitrogen-containing heterocyclic ring. Examples of the hetero ring include the following heterocyclic rings.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ^11b include a benzyl group, a phenylethyl group, and a phenylbutyl group.

Zb ⁺ is ⁺ N(R ^11b ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ^11b ) ₄ .

As the above ⁺ N(R ^11b ) ₄ , at least two of the four R ^11b are preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ^11b is preferably from 20 to 80, and more preferably from 20 to 60.

Examples of Xb include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom and a bromine atom are preferable, and a chlorine atom is more preferable.

b is 0 or 1, preferably 0.

In addition, as the compound represented by the formula (1a-1), for example, a compound represented by the following formula (1c) (hereinafter sometimes referred to as "compound (1c)")) is preferable. The compound (1c) may be a tautomer thereof.

In the formula (1c), R ^1c and R ^4c independently of each other represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms or an alkylsulfonyl group having 1 to 4 carbon atoms.

p and q independently represent an integer of 0 to 5. When p is 2 or more, a plurality of R ^1c may be the same or different, and when q is 2 or more, a plurality of R ^4c may be the same or different.

R ^2c and R ^3c independently of each other represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and in R ^2c and R ^3c , -CH ₂ - contained in the saturated hydrocarbon group may be - O-, -CO-, -NR ^11c -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-. However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

R ^1c and R ^2c may together form a ring containing a nitrogen atom, and R ^3c and R ^4c may together form a ring containing a nitrogen atom.

R ^5c represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Zc ⁺ , -CO ₂ H, -CO ₂ ^- Zc ⁺ , -CO ₂ R ^8c , -SO ₃ R ^8c or -SO ₂ NR ^9c R ^10c .

R ^6c and R ^7c independently of each other represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Mc represents an integer from 0 to 5. When mc is 2 or more, a plurality of R ^5c may be the same or different.

c represents an integer of 0 or 1.

Xc represents a halogen atom.

Zc ⁺ represents ⁺ N(R ^11c ) ₄ , Na ⁺ or K ⁺ , and the four R ^11c may be the same or different.

R ^8c represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom.

R ^9c and R ^10c independently of each other represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO-, -NR ^11c -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-, R ^9c and R ^10c may be bonded to each other to form a 3 to 10 membered ring containing a nitrogen atom. Heterocyclic. However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

R ^11c represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. ]

In the formula (1c), when -SO ₃ ^{- is} present, the number is one.

Examples of the alkyl group having 1 to 4 carbon atoms in R ^1c and R ^4c include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.

Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ^1c and R ^4c include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, and an isopropyl group. Sulfuryl group and the like.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ^1c and R ^4c include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropyl group. Sulfonyl and the like.

R ^1c and R ^{4c are} preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

p and q are preferably an integer of 0 to 2, preferably 1 or 2.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ^2c , R ^3c and R ^8c to R ^11c include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Linear alkyl groups such as octyl, decyl, decyl, dodecyl, hexadecyl and eicosyl; isopropyl, isobutyl, isopentyl, neopentyl and 2-ethyl a branched chain alkyl group such as a hexyl group; an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group.

-CH ₂ - contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, -NR ^11c -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO- . However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

The hydrogen atom contained in the saturated hydrocarbon group in R ^2c and R ^3c may be substituted with, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom as a substituent. Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with a hydrogen atom of a saturated hydrocarbon group of R ^2c and R ^3c include a group exemplified as an aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ . The same group of the group.

The hydrogen atom contained in the saturated hydrocarbon group in R ^9c and R ^10c may be substituted with, for example, a hydroxyl group or a halogen atom as a substituent.

Examples of -OR ^8c include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group and two. An alkoxy group such as a decadecyloxy group.

Examples of the -CO ₂ R ^8c include alkoxycarbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group and an eicosyloxycarbonyl group.

Examples of -SR ^8c include alkylsulfane groups such as methylsulfanyl group, ethylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, mercaptosulfanyl group, and eicosylsulfanyl group. Base.

Examples of the -SO ₂ R ^8c include an alkyl group such as a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a nonylsulfonyl group, and an eicosylsulfonyl group. Sulfonyl and the like.

Examples of -SO ₃ R ^8c include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an eicosane. An alkoxysulfonyl group such as oxysulfonyl group.

Examples of -SO ₂ NR ^9c R ^10c include an aminesulfonyl group; N-methylaminesulfonyl group, N-ethylaminesulfonyl group, N-propylaminesulfonyl group, and N-isopropyl group; Amine sulfonyl, N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-sec-butylamine sulfonyl, N-tert-butylamine sulfonyl, N-pentylamine Sulfonyl, N-(1-ethylpropyl)aminesulfonyl, N-(1,1-dimethylpropyl)aminesulfonyl, N-(1,2-dimethylpropyl) Aminesulfonyl, N-(2,2-dimethylpropyl)aminesulfonyl, N-(1-methylbutyl)aminesulfonyl, N-(2-methylbutyl)aminesulfonate Mercapto, N-(3-methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, N-hexylamine sulfonyl, N-(1,3-dimethylbutyl)amine Sulfosyl, N-(3,3-dimethylbutyl)amine sulfonyl, N-heptylamine sulfonyl, N-(1-methylhexyl)amine sulfonyl, N-(1, 4-dimethylpentyl)amine sulfonyl, N-octylamine sulfonyl, N-(2-ethylhexyl)amine sulfonyl, N-(1,5-dimethylhexyl)amine sulfonate N-1 substituted amine sulfonyl group such as fluorenyl, N-(1,1,2,2-tetramethylbutyl)amine sulfonyl group; N,N-dimethylamine sulfonyl group, N,N- Ethylmethylamine sulfonyl, N,N-diethylamine sulfonyl, N,N- Methylamine sulfonyl, N,N-isopropylmethylamine sulfonyl, N,N-tert-butylmethylamine sulfonyl, N,N-butylethylamine sulfonyl, N,N An N,N-2 substituted amine sulfonyl group such as bis(1-methylpropyl)amine sulfonyl group or N,N-heptylmethylamine sulfonyl group.

As R ^5c , preferably -CO ₂ H, -CO ₂ ^- Zc ⁺ , -CO ₂ R ^8c , -SO ₃ ^- , -SO ₃ ^- Zc ⁺ , -SO ₃ H or -SO ₂ NHR ^9c , more preferably -SO ₃ ^- , -SO ₃ ^- Zc ⁺ , -SO ₃ H or -SO ₂ NHR ^9c .

Mc is preferably 1 to 4, more preferably 1 or 2.

In the compound (1c), the phenyl group substituted with the (R ^5c ) _mc group is preferably any one of the above (R ⁵ -1) to (R ^{5 -} 37), and more preferably (R ⁵ -1) to (R). Any one of ^{5 to} 25) is more preferably (R ⁵ -1) to (R ⁵ -5), and particularly preferably (R ⁵ -1).

The alkyl group having 1 to 6 carbon atoms in R ^6c and R ^7c may, for example, be an alkyl group having 1 to 6 carbon atoms in the above-exemplified alkyl group. Among them, as R ^6c and R ^7c , a hydrogen atom is preferred.

R ^9c and R ^10c may together with a nitrogen atom represent a 3 to 10 membered nitrogen-containing heterocyclic ring. Examples of the hetero ring include the following heterocyclic rings.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ^11c include a benzyl group, a phenylethyl group, and a phenylbutyl group.

Zc ⁺ is ⁺ N(R ^11c ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ^11c ) ₄ .

As the above ⁺ N(R ^11c ) ₄ , at least two of the four R ^11c are preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ^11c is preferably 20 to 80, and more preferably 20 to 60.

Xc is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

c is 0 or 1, more preferably 0.

In addition, as the compound represented by the formula (1a-2), for example, a compound represented by the following formula (1d) (hereinafter sometimes referred to as "compound (1d)")) is preferable. The compound (1d) may be a tautomer thereof.

In the formula (1d), R ^1d to R ^4d independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a monovalent carbon having 6 to 10 carbon atoms which may have a substituent. The aromatic hydrocarbon group or the group represented by the formula (ii), at least one of R ^1d to R ^4d is a group represented by the formula (ii).

*-R ⁵⁰ -Si(R ²⁹ ) ₃ (ii)

(R ²⁹ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and a plurality of R ^{29 's} may be the same or different.

R ⁵⁰ represents an alkylene group having 1 to 10 carbon atoms, and -CH ₂ - constituting the alkylene group may be -O-, -CO-, -NR ^11d -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO- replacement. However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

* indicates the bonding end with a nitrogen atom. )

In R ^1d to R ^4d , -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO-, -NR ^11d -, -OCO-, -COO-, -OCONH-, -NHCOO-, - In the case of CONH- or -NHCO-, R ^1d and R ^2d may together form a ring containing a nitrogen atom, and R ^3d and R ^4d may together form a ring containing a nitrogen atom. However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

R ^5d represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Zd ⁺ , -CO ₂ H, -CO ₂ ^- Zd ⁺ , -CO ₂ R ^8d , -SO ₃ R ^8d or -SO ₂ NR ^9d R ^10d .

R ^6d and R ^7d independently of each other represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Md represents an integer from 0 to 5. When md is 2 or more, a plurality of R ^5d may be the same or different.

d represents an integer of 0 or 1.

Xd represents a halogen atom.

Zd ⁺ represents ⁺ N(R ^11d ) ₄ , Na ⁺ or K ⁺ , and the four R ^11d may be the same or different.

R ^8d represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom.

R ^9d and R ^10d independently of each other represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO-, -NR ^11d -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-, R ^9d and R ^10d may be bonded to each other to form a 3 to 10 membered ring containing a nitrogen atom. Heterocyclic. However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

R ^11d represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. ]

In the formula (1d), in the case where -SO ₃ ^{- is} present, the number thereof is one.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^1d to R ^4d include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group. .

Examples of the substituent which the aromatic hydrocarbon group may have include a halogen atom, -R ^8d , -OH, -OR ^8d , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Zd ⁺ , -CO ₂ H, -CO ₂ R ^8d , -SR ^8d , -SO ₂ R ^8d , -SO ₃ R ^8d or -SO ₂ NR ^9d R ^10d , preferably these substituents are substituted with a hydrogen atom contained in the aromatic hydrocarbon group. Among these, as a substituent group, preferably _{^{-SO 3 -, -SO 3 H,}} -SO 3 - Zd + and -SO ₂ NR ^9d R ^10d, more preferably -SO ₃ ^- Zd ⁺ and -SO ₂ NR ^9d R ^10d. As -SO ₃ ^- Zd ^{+ in} this case, -SO ₃ ^-+ N(R ^11d ) ₄ is preferable.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ^1d to R ^4d and R ^8d to R ^11d include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. a linear alkyl group such as octyl, decyl, decyl, dodecyl, hexadecyl or eicosyl; isopropyl, isobutyl, isopentyl, neopentyl, 2-ethyl a branched chain alkyl group such as a hexyl group; an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a tricyclodecyl group.

-CH ₂ - contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, -NR ^11d -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO- . However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

The hydrogen atom contained in the saturated hydrocarbon group in R ^1d to R ^4d may be substituted with, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom as a substituent. The aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with a hydrogen atom of a saturated hydrocarbon group of R ^1d to R ^4d may be exemplified as the aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^1d to R ^4d . The same group of the group.

The hydrogen atom contained in the saturated hydrocarbon group in R ^9d and R ^10d may be substituted, for example, by a hydroxyl group or a halogen atom as a substituent.

Examples of the ring formed by R ^1d and R ^2d together with the ring formed by R ^3d and R ^4d include the following rings.

At least one of R ^1d to R ^4d is a group represented by the formula (ii), and as other R ^1d to R ^4d , a methyl group, an ethyl group, a propyl group, a 1-methylphenyl group, a 1,5- group is preferable. Dimethylphenyl, more preferably methyl, ethyl or propyl.

Examples of -OR ^8d include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group and two. An alkoxy group such as a decadecyloxy group.

Examples of the -CO ₂ R ^8d include alkoxycarbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a t-butoxycarbonyl group, a hexyloxycarbonyl group, and an eicosyloxycarbonyl group.

Examples of the -SR ^8d include alkylsulfane groups such as methylsulfanyl group, ethylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, mercaptosulfanyl group, and eicosylsulfanyl group. Base.

Examples of the -SO ₂ R ^8d include an alkyl group such as a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an eicosylsulfonyl group. Sulfonyl and the like.

Examples of -SO ₃ R ^8d include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an eicosane. An alkoxysulfonyl group such as oxysulfonyl group.

Examples of the -SO ₂ NR ^9d R ^10d include an aminesulfonyl group, an N-methylaminesulfonyl group, an N-ethylaminesulfonyl group, an N-propylaminesulfonyl group, and an N-isopropyl group. Amine sulfonyl, N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-sec-butylamine sulfonyl, N-tert-butylamine sulfonyl, N-pentylamine Sulfonyl, N-(1-ethylpropyl)aminesulfonyl, N-(1,1-dimethylpropyl)aminesulfonyl, N-(1,2-dimethylpropyl) Aminesulfonyl, N-(2,2-dimethylpropyl)aminesulfonyl, N-(1-methylbutyl)aminesulfonyl, N-(2-methylbutyl)aminesulfonate Mercapto, N-(3-methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, N-hexylamine sulfonyl, N-(1,3-dimethylbutyl)amine Sulfosyl, N-(3,3-dimethylbutyl)amine sulfonyl, N-heptylamine sulfonyl, N-(1-methylhexyl)amine sulfonyl, N-(1, 4-dimethylpentyl)amine sulfonyl, N-octylamine sulfonyl, N-(2-ethylhexyl)amine sulfonyl, N-(1,5-dimethylhexyl)amine sulfonate N-1 substituted amine sulfonyl group such as fluorenyl, N-(1,1,2,2-tetramethylbutyl)amine sulfonyl group; N,N-dimethylamine sulfonyl group, N,N- Ethylmethylamine sulfonyl, N,N-diethylamine sulfonyl, N,N- Methylamine sulfonyl, N,N-isopropylmethylamine sulfonyl, N,N-tert-butylmethylamine sulfonyl, N,N-butylethylamine sulfonyl, N,N An N,N-2 substituted amine sulfonyl group such as bis(1-methylpropyl)amine sulfonyl group or N,N-heptylmethylamine sulfonyl group.

As R ^5d , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ^8d , -SO ₃ ^- , -SO ₃ ^- Zd ⁺ , -SO ₃ H or -SO ₂ NHR ^9d are preferred, and -SO is more preferred. ₃ ^- , -SO ₃ ^- Zd ⁺ , -SO ₃ H or -SO ₂ NHR ^9d .

The md is preferably from 1 to 4, more preferably 1 or 2.

In the formula (1d), the phenyl group substituted by the (R ^5d ) _md group is preferably any one of the above formulas (R ⁵ -1) to (R ⁵ -37), and more preferably ( Any one of R ⁵ -1) to (R ⁵ -25) is more preferably (R ⁵ -1) to (R ⁵ -5), and particularly preferably (R ⁵ -1).

Examples of the alkyl group having 1 to 6 carbon atoms in R ^6d and R ^7d include an alkyl group having 1 to 6 carbon atoms in the above-exemplified alkyl group. Among them, as R ^6d and R ^7d , a hydrogen atom is preferred.

R ^9d and R ^10d may together with a nitrogen atom represent a 3 to 10 membered nitrogen-containing heterocyclic ring. Examples of the hetero ring include the following heterocyclic rings.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ^11d include a benzyl group, a phenylethyl group, and a phenylbutyl group.

Zd ⁺ is ⁺ N(R ^11d ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ^11d ) ₄ .

As the above ⁺ N(R ^11d ) ₄ , at least two of the four R ^11d are preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ^11d is preferably 20 to 80, and more preferably 20 to 60.

Xd is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

d is 0 or 1, more preferably 0.

Further, the substituent represented by the formula (ii) in R ^1d to R ^4d is the same as the substituent described in detail in the formula (1a).

Among the above-mentioned xanthene dyes (1d), a more preferable compound is, for example, a compound represented by the following formula (2d):

In the formula (2d), R ^1d to R ^4d independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or a formula (ii) The group represented by the formula, at least one of R ^1d to R ^4d is a group represented by the formula (ii).

*-R ⁵⁰ -Si(R ²⁹ ) ₃ (ii)

(R ²⁹ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and a plurality of R ^{29 's} may be the same or different.

R ⁵⁰ represents an alkylene group having 1 to 10 carbon atoms, and -CH ₂ - constituting the alkylene group may be -O-, -CO-, -NR ^11d -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO- substitution. However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

* indicates the bonding end with a nitrogen atom. )

In R ^1d to R ^4d , -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO-, -NR ^11d -, -OCO-, -COO-, -OCONH-, -NHCOO-, - In place of CONH- or -NHCO-, R ^1d and R ^2d may together form a ring containing a nitrogen atom, and R ^3d and R ^4d may together form a ring containing a nitrogen atom. However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

R ^5d represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Zd ⁺ , -CO ₂ H, -CO ₂ ^- Zd ⁺ , -CO ₂ R ^8d , -SO ₃ R ^8d or -SO ₂ NR ^9d R ^10d .

R ^6d and R ^7d independently of each other represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Md represents an integer from 0 to 5. When md is 2 or more, a plurality of R ^5d may be the same or different.

d represents an integer of 0 or 1.

Xd represents a halogen atom.

Zd ⁺ represents ⁺ N(R ^11d ) ₄ , Na ⁺ or K ⁺ , and the four R ^11d may be the same or different.

R ^8d represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom.

R ^9d and R ^10d independently of each other represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO-, -NR ^11d -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO- instead, R ^9d and R ^10d may be bonded to each other to form a 3 to 10 membered ring containing a nitrogen atom. Heterocyclic. However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

R ^11d represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. ]

More preferably, it is a compound represented by the following formula (3d).

In the formula (3d), R ^1d to R ^4d each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or a formula (i) The group represented by the formula, at least one of R ^1d to R ^4d is a group represented by the formula (i).

(In the formula (i), n represents an integer of 1 to 8, and R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the plurality of OR ¹² may be the same or different.

* indicates the bonding end with a nitrogen atom. )

In R ^1d to R ^4d , -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO-, -NR ^11d -, -OCO-, -COO-, -OCONH-, -NHCOO-, - In place of CONH- or -NHCO-, R ^1d and R ^2d may together form a ring containing a nitrogen atom, and R ^3d and R ^4d may together form a ring containing a nitrogen atom. However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

R ^5d represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Zd ⁺ , -CO ₂ H, -CO ₂ ^- Zd ⁺ , -CO ₂ R ^8d , -SO ₃ R ^8d or -SO ₂ NR ^9d R ^10d .

R ^6d and R ^7d independently of each other represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Md represents an integer from 0 to 5. When md is 2 or more, a plurality of R ^5d may be the same or different.

d represents an integer of 0 or 1.

Xd represents a halogen atom.

Zd ⁺ represents ⁺ N(R ^11d ) ₄ , Na ⁺ or K ⁺ , and the four R ^11d may be the same or different.

R ^8d represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom.

R ^9d and R ^10d independently of each other represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO-, -NR ^11d -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-, R ^9d and R ^10d may be bonded to each other to form a 3 to 10 membered ring containing a nitrogen atom. Heterocyclic. However, the adjacent -CH ₂ - will not be replaced by the same group at the same time, and the -CH ₂ - at the end will not be replaced.

R ^11d represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. ]

The compound represented by the following formula (I-1) to (I-170) is exemplified as a preferable compound of the above-mentioned xanthene dye (1a). In the formula, R ⁴⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms, and more preferably 2-ethylhexyl group.

In the case of the xanthene dye (1a), for example, one substituent represented by the formula (ii) is present in R ¹ to R ⁴ , and the remaining group is a carbon number of 1 to 20 which may have a substituent. a valence saturated hydrocarbon group compound (for example, compounds (I-1) to (I-4), (I-13) to (I-16), (I-25) to (I-28), (I-37) )~(I-40), (I-55)~(I-110), (I-117), (I-120), etc.), two of R ¹ to R ⁴ are represented by formula (ii) The substituent and the remaining group are a compound having a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (for example, the compound (I-49) to (I-54) and the compound (I-111). (I-116), compound (I-119), (I-121), (I-122)), a compound having two xylyl groups in R ¹ to R ⁴ (for example, compound (I-124) ~(I-146), (I-151), (I-153), (I-155), (I-156), etc.), a compound having two tolyl groups in R ¹ to R ⁴ (for example, The compound (I-147), (I-150), (I-152), (I-154), etc.), and all of R ¹ to R ⁴ are a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. Compound (for example, compound (I-160)~(I-170), etc.).

Further preferred are the compounds (I-1) to (I-4), (I-13) to (I-16), (I-25) to (I-28), (I-50), (I-51). ), (I-53), (I-54), (I-119), (I-121), (I-122), (I-124)~(I-147), (I-150)~ (I-156), (I-160)~(I-167).

For the xanthene dye (a), a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink R-H/C" manufactured by Nakagata Kasei Co., Ltd., or "Rhodamin 6G" manufactured by Tajika Chemical Industry Co., Ltd.) can be used. In addition, the commercially available xanthene dye can be used as a starting material, and it can be synthesized by referring to JP-A-2010-32999.

Examples of such a xanthene dye (a) include CI Acid Red 51 (hereinafter, the description of CI Acid Red is omitted, only the serial number is described. Others are the same), and CIs such as 52, 87, 92, 94, 289, and 388 are used. Acid red dye; CI acid violet 9, 30, 102, etc. CI acid violet dye; CI basic red 1 (Rhodamine 6G), 2, 3, 4, 8, 10 (Rhodamine B), 11 and other CI base Red dye; CI alkaline violet 10, 11, 25 and other CI alkaline violet dye; CI solvent red 218 and other CI solvent red dye; CI mordant red 27 and other CI mordant red dye; CI active red 36 (Rose red B), etc. CI reactive red dye; sulfo rhodamine G; xanthene dyes described in Japanese Laid-Open Patent Publication No. 2010-32999; and xanthene dyes described in Japanese Patent No. 4492760.

The xanthene dye (a) is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, even more preferably 1 to 10% by mass, based on 100% by mass of the dye solution.

<salt of organic acid>

The salt of the organic acid used in the present invention is, for example, an aliphatic carboxylic acid, an aromatic carboxylic acid, an aliphatic sulfonic acid, an alicyclic sulfonic acid or an aromatic sulfonic acid, which is represented by the following formula (h1). a salt of an organic acid of at least one of a compound and a compound represented by the following formula (h2), which constitutes an acid of the above aliphatic carboxylic acid, the above aromatic carboxylic acid, the above aliphatic sulfonic acid, and the above aromatic sulfonic acid The hydrogen atom other than the proton may be substituted by a halogen atom, a hydroxyl group or the like, and -CH ₂ - constituting the above aliphatic carboxylic acid, aliphatic sulfonic acid, and the above alicyclic sulfonic acid may be replaced by -CO-.

[In the formula (h1), X ^h1 and X ^h2 independently of each other represent a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms, or X ^h1 and X ^{h2 are} combined to form a fluoroalkylene group having 2 to 4 carbon atoms; base.

In the formula (h2), X ^h3 to X ^h5 independently represent a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms. ]

The aliphatic carboxylic acid means a compound R ²¹ (COOH) _x having a carboxyl group (-COOH) (x is an integer of 1 or more, more preferably 1, 2 or 3, further preferably 1 or 2), and R ²¹ is an aliphatic group. Hydrocarbyl carboxylic acid, or formic acid. Examples of such an aliphatic carboxylic acid include a saturated fatty acid having 1 to 25 carbon atoms and an unsaturated carboxylic acid having 1 to 25 carbon atoms. Examples of the saturated fatty acid having 1 to 25 carbon atoms include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, and lauric acid; An aliphatic dicarboxylic acid such as malonic acid, succinic acid, glutaric acid or adipic acid. Further, examples of the unsaturated carboxylic acid having 1 to 25 carbon atoms include oleic acid, linoleic acid, linolenic acid, arachidonic acid, docosahexaenoic acid, eicosapentaenoic acid, and Fumar. Acid, maleic acid, etc.

The aromatic carboxylic acid means a compound R ²² (COOH) _x having a carboxyl group (-COOH) (x is an integer of 1 or more, more preferably 1, 2 or 3, further preferably 1 or 2), and R ²² is aromatic. Hydrocarbyl carboxylic acid. The R ²² may be an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and more preferably a phenyl group which may have a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. Examples of such an aromatic carboxylic acid include benzoic acid, toluic acid, dimethylbenzoic acid, diethylbenzoic acid, dipropylbenzoic acid, dibutylbenzoic acid, phthalic acid, and isophthalic acid. Formic acid, terephthalic acid, naphthalene dicarboxylic acid, and the like.

Examples of the alicyclic sulfonic acid include cyclohexanesulfonic acid, 4-methylcyclohexanesulfonic acid, and bicyclo[2.2.1]-hept-2-ene-5-sulfonic acid.

The aliphatic sulfonic acid means a compound R ²³ (SO ₃ H) _x having a sulfo group (-SO ₃ H) (x is an integer of 1 or more, more preferably 1, 2 or 3, further preferably 1 or 2) R ²³ is an aliphatic hydrocarbon group sulfonic acid. Examples of such an aliphatic sulfonic acid include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, valeric acid, hexanesulfonic acid, heptanoic acid, octanesulfonic acid, sulfonic acid, and sulfonium. An aliphatic monosulfonic acid such as an acid; an aliphatic disulfonic acid such as methane disulfonic acid, ethane disulfonic acid, propane disulfonic acid, butane disulfonic acid, pentane disulfonic acid or hexane disulfonic acid; and the like.

The aromatic sulfonic acid means a compound R ²⁴ (SO ₃ H) _x having a sulfo group (-SO ₃ H) (x is an integer of 1 or more, more preferably 1, 2 or 3, further preferably 1 or 2) R ²⁴ is an aromatic hydrocarbon group sulfonic acid. Examples of such an aromatic sulfonic acid include benzenesulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid.

A hydrogen atom other than the acidic proton constituting the aliphatic carboxylic acid, the aromatic carboxylic acid, the aliphatic sulfonic acid, and the aromatic sulfonic acid may be substituted with a halogen atom or a hydroxyl group. Examples of the halogen atom which may be substituted with a hydrogen atom other than the acidic proton in the aliphatic carboxylic acid, the aromatic carboxylic acid, the aliphatic sulfonic acid, and the aromatic sulfonic acid include F, Cl, Br, and I. Among them, fluorine is preferred. Examples of such an acid include lactic acid, malic acid, citric acid, salicylic acid, and 3,5-di-tert-butylsalicylic acid.

The -CH ₂ - constituting the aliphatic carboxylic acid, the aliphatic sulfonic acid, and the alicyclic sulfonic acid may be replaced by -CO-, and examples of the acid include 10-camphorsulfonic acid.

Further, in the above formula (h1), X ^h1 and X ^h2 are each independently a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms. Further, in the above formula (h2), X ^h3 to X ^h5 independently represent a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms.

Examples of the fluoroalkyl group having 1 to 4 carbon atoms include the following substituents, and among them, *-CF ₂ CF ₃ , *-CF ₂ CF ₂ CF ₃ and *-CF ₂ CF ₂ CF are preferable. ₂ CF ₃ , more preferably *-CF ₂ CF ₂ CF ₃ and *-CF ₂ CF ₂ CF ₂ CF ₃ .

Further, in the case of X ^h1 and X ^h2 , X ^h1 and X ^h2 may be combined to form a fluoroalkylene group having 2 to 4 carbon atoms. As the fluoroalkylene group having 2 to 4 carbon atoms, for example, a substituent represented by *-(CF ₂ ) _n -* (wherein n is an integer of 2 to 4) is preferable.

Examples of the salt of the various organic acids include an alkali metal salt such as a lithium salt, a sodium salt, a potassium salt or a phosphonium salt; an alkaline earth metal salt such as a calcium salt; a metal salt such as a zinc salt or a copper salt; and a quaternary ammonium salt. .

As a salt of such an organic acid, for example, a salt of a benzoic acid which may have a substituent represented by the following formulas (h0-1) to (h0-21), and the following formula (h1-1) to (h1-) are preferable. 8) a compound shown and a compound represented by the following formula (h2-1) to (h2-8).

The salt of the compound represented by the above formula (h0-13), the compound represented by the above formula (h1), or the compound represented by the above formula (h2) is more preferable, and the above formula (h0) is more preferable. -13) a zinc salt, lithium bis(trifluoromethanesulfonyl)imide, or tris(trifluoromethanesulfonyl)methylene ylide lithium.

<compound containing a ruthenium atom>

Examples of the compound containing a ruthenium atom include a compound represented by the following formula (j). In the present invention, the "compound containing a ruthenium atom" also includes a "condensate" of a compound represented by the following formula (j).

[Chemical Formula 81] R ^h2 -Si-(R ^h1 ) ₃ (j)

In the formula (j), R ^h1 represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and a plurality of ^Rh1 may be the same or different, and ^{Rh 2} represents a monovalent group. Substituent.

Examples of the alkyl group having 1 to 4 carbon atoms in R ^h1 include a methyl group, an ethyl group, a propyl group, and a butyl group. These may be linear or branched.

Examples of the alkoxy group having 1 to 4 carbon atoms in R ^h1 include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. From the viewpoint of contributing to stability over time, a methoxy group and an ethoxy group are preferred, and an ethoxy group is more preferred.

Among them, as R ^h1 , a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms is more preferable, and an alkoxy group having 1 to 4 carbon atoms is particularly preferable.

R ^h2 is a monovalent substituent. R ^h2 is preferably a saturated hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group selected from the group consisting of a vinyl group, an epoxy group, a methacryl group, an acryl group, and an amine group. A substituent of a functional group of at least one of an isocyanurate group, a ureido group, a thiol group, a thioether group, and an isocyanate group. The functional group contained in R ^h2 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 10 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms in the compound (j) containing a halogen atom. Combine.

As R ^h2 carbon atoms a saturated hydrocarbon group having 1 to 10 carbon atoms are preferred saturated hydrocarbon group having 2 to 9, more preferably a carbon number of a saturated hydrocarbon group having 4 to 8, more preferably pentyl group, hexyl group, heptyl group or octyl. A halogen atom, a hydrogen atom constituting the saturated hydrocarbon group may be a fluorine atom, a chlorine atom, or * -Si (R ^h3) ₃ and the like substituent group (R ^h3 is alkoxy having 1 to 4 in the above formula,) group.

The aromatic hydrocarbon group having 6 to 10 carbon atoms of R ^{h2 is} , for example, a phenyl group.

The divalent saturated hydrocarbon group having 1 to 10 carbon atoms contained in R ^h2 is preferably a saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms. Saturated hydrocarbon group.

As the divalent aromatic hydrocarbon group having 6 to 10 carbon atoms contained in ^Rh 2 , for example, a phenylene group is preferable.

As such R ^h2 , for example, a substituent shown below is preferable, and as R ^h2 , 3-methylpropenyloxypropyl group, N-methyl-3-aminopropyl group, and N-phenyl group are preferable. 3-aminopropyl and octyl.

Examples of such a ruthenium atom-containing compound include a decane coupling agent and a decane compound.

Examples of the decane coupling agent include vinyl decane coupling agents such as vinyl trimethoxy decane and vinyl triethoxy decane; and 2-(3,4-epoxycyclohexyl)ethyltrimethoxy. Decane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-shrinkage An epoxy-based decane coupling agent such as glyceryloxypropyltriethoxydecane; a styryl decane coupling agent such as p-styryltrimethoxydecane; 3-methylpropenyloxypropylmethyl Dimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyl three (Meth) propylene fluorenyl decane coupling agent such as ethoxy decane or 3-propenyl methoxy propyl trimethoxy decane; N-2-(aminoethyl)-3-aminopropylmethyl Dimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane 3-triethoxycarbamido-N-(1,3-dimethyl Base-butylidene)propylamine, N-methyl-3-aminopropyltrimethoxysulfonium Amino-based decane coupling agent such as alkane or N-phenyl-3-aminopropyltrimethoxydecane; urea-based decane coupling agent such as 3-ureidopropyltrialkoxydecane; 3-mercaptopropyl acrylate a mercapto-based decane coupling agent such as methyl dimethoxy decane or 3-mercaptopropyl trimethoxy decane; a thioether decane coupling agent such as bis(triethoxymethane alkylpropyl) tetrasulfide; An isocyanate-based decane coupling agent such as 3-isocyanatepropyltriethoxydecane.

Further, examples of the decane compound include methyltrimethoxydecane, dimethyldimethoxydecane, phenyltrimethoxydecane, methyltriethoxydecane, and dimethyldiethoxydecane. Phenyltriethoxydecane, propyltrimethoxydecane, propyltriethoxydecane, hexyltrimethoxydecane, hexyltriethoxydecane,octyltrimethoxydecane,octyltriethoxydecane An alkoxy decane such as mercaptotrimethoxydecane, mercaptotriethoxydecane or 1,6-bis(trimethoxyformamido)hexane.

Among them, as the compound containing a halogen atom, a (meth)acrylonitrile-based decane coupling agent, an amine-based decane coupling agent, an alkoxydecane, and more preferably a 3-methylpropenyloxypropylmethyl group are preferable. Dimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyl three Ethoxy decane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, N-methyl-3-aminopropyltrimethoxydecane, N-phenyl-3 -Aminopropyltrimethoxydecane, propyltrimethoxydecane, propyltriethoxydecane,hexyltrimethoxydecane,hexyltriethoxydecane,octyltrimethoxydecane,octyltriethoxy More preferably, 3-decyloxypropyltrimethoxydecane, N-methyl-3-aminopropyl, 3-decyloxypropyltrimethoxydecane Trimethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, hexyltrimethoxydecane, hexyltriethoxydecane, octyltrimethoxydecane, octyltriethoxydecane, especially Preferred is 3-methacryloxypropyltrimethoxydecane, N-methyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, octane Trimethoxy decane.

The amount of the compound containing a halogen atom is preferably 20 to 500 parts by mass, more preferably 50 to 300 parts by mass, even more preferably 80 to 200 parts by mass, per 100 parts by mass of the xanthene dye (a).

In addition, when the salt of the organic acid and the compound containing a ruthenium atom are used in combination as the component (b), the amount of the organic acid salt used is preferably 1 in total based on 100 parts by mass of the xanthene dye. ~50 parts by mass, more preferably 5 to 40 parts by mass, still more preferably 10 to 30 parts by mass. In addition, the amount of the compound containing a halogen atom is preferably 200 to 1000 parts by mass, more preferably 300 to 800 parts by mass, even more preferably 400 to 700 parts by mass, based on 100 parts by mass of the total amount of the salt of the organic acid. .

<organic solvent>

The organic solvent to be used in the present invention is not particularly limited as long as it can dissolve the above-mentioned xanthene dye (a), and examples thereof include an ester solvent (containing -COO- in the molecule, and -O-free). - a solvent), an ether solvent (a solvent containing -O- in the molecule, a solvent containing no -COO-), an ether ester solvent (a solvent containing -COO- and -O- in the molecule), a ketone solvent (in the molecule) A solvent containing -CO-, without -COO-), an alcohol solvent (a solvent containing OH in the molecule, a solvent containing no -O-, -CO-, and -COO-), an aromatic hydrocarbon solution Agent, guanamine solvent, dimethyl hydrazine and the like.

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

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, and diethylene glycol. Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3- Methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether , diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether, methyl anisole and the like.

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

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

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

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and 1,3,5-trimethylbenzene.

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

These solvents may be used alone or in combination of two or more. Among them, an ether ester solvent, a ketone solvent, an alcohol solvent, and a mixed solvent thereof are preferably used, and an ether ester solvent, a ketone solvent, and a mixed solvent thereof are more preferably used.

As the ether ester solvent, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ester are preferable. An alkylene glycol monoalkyl ether carboxylate such as an ether acetate, more preferably propylene glycol monomethyl ether acetate.

As the ketone solvent, an aliphatic alcohol having a ketocarbonyl group is preferred, and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone) is more preferred.

<Production of dye solution>

In the present invention, at least one of a salt of an organic acid and a compound containing a ruthenium atom may be used as the component (b), and only one selected from the group consisting of a salt selected from an organic acid and a compound containing a ruthenium atom may be used. a salt selected from organic acids Two or more kinds of compounds containing a halogen atom are used in combination. Examples of the use of the component (b) include a method of using a salt of an organic acid, a method of using only a compound containing a ruthenium atom, and a combination of a salt of an organic acid and a compound containing a ruthenium atom. Ways, etc.

In the method of using a salt of an organic acid or a compound containing only a ruthenium atom, the method for preparing the composition (mixture) containing the (a) xanthene dye and the component (b) is not particularly limited. The preparation method of the composition may, for example, be a method of adding (a) a xanthene dye to a mixed solution containing the component (b) and an organic solvent; and adding it in a mixed solution containing (a) a xanthene dye and an organic solvent ( b) method of ingredients, etc.

In the method of using a combination of a salt of an organic acid and a compound containing a ruthenium atom, the method of adding xanthene (a) and a compound containing a ruthenium atom is not particularly limited, and examples thereof include a salt of an organic acid. a method of adding a xanthene-containing dye (a) after stirring with a compound containing a ruthenium atom (referred to as a stirring step 1); adding a xanthene dye (a) in the presence of a salt of an organic acid and stirring (referred to as The stirring step 2) a method of adding a compound containing a ruthenium atom; a method of adding a xanthene dye (a) and a compound containing a ruthenium atom in the presence of a salt of an organic acid.

In the stirring steps 1 to 2, the stirring time is, for example, 30 minutes or longer, preferably 1 hour or longer, more preferably 2 hours or longer, and the upper limit is not particularly limited, but is usually 20 hours or shorter.

In addition, in order to increase the solubility of a compound containing a ruthenium atom in an organic solvent, it may be added before the addition of a compound containing a ruthenium atom. In any of the additions, the mixture is heated to 30 to 60 °C.

The thus obtained composition containing at least one of (a) xanthene dye, and (b) a salt selected from an organic acid and a halogen atom-containing compound is stirred in the presence of an organic solvent.

The stirring time is not particularly limited, and is, for example, preferably 1 hour or longer, more preferably 3 hours or longer, further preferably 5 hours or longer, particularly preferably 10 hours or longer, preferably 100 hours or shorter, more preferably 90 hours or shorter, further preferably It is 80 hours or less, particularly preferably 60 hours or less, still more preferably 40 hours or less, and still more preferably 30 hours or less.

Further, when the xanthene dye (a) is treated with only a salt of an organic acid, the stirring time is, for example, preferably 2 hours or longer, more preferably 3 hours or longer, preferably 80 hours or shorter, more preferably 60 hours or shorter, and still more preferably It is 40 hours or less, and it is especially preferable to be 30 hours or less.

In addition, when the xanthene dye (a) is treated with only a compound containing a halogen atom or a combination of a salt of an organic acid and a compound containing a halogen atom, the stirring time is preferably, for example, 5 hours or more. It is preferably 10 hours or longer, preferably 30 hours or shorter, more preferably 20 hours or shorter.

The stirring temperature is not particularly limited, and is, for example, preferably -10 ° C or higher, more preferably 0 ° C or higher, further preferably 10 ° C or higher, particularly preferably 20 ° C or higher, preferably 80 ° C or lower, more preferably 70 ° C or lower, and still more preferably 60 ° C or lower. .

<Solid-liquid separation process>

In the present invention, after the stirring step, a solid-liquid separation step for removing insoluble matter can be performed. Examples of the solid-liquid separation include filtration, Centrifugal separation, and combinations thereof, are particularly preferably carried out in the present invention from the viewpoint of ease of handling. Examples of the filtration method include natural filtration, pressure filtration, and reduced pressure filtration.

A filter aid can be used in the filtration. The filter aid can be used in either the precoat or bulk feed. Examples of the filter aid include activated clay, ceria, diatomaceous earth, Celite, pearlite, cellulose, activated carbon, alumina, magnesium niobate, aluminum hydroxide, hydrotalcite, aluminum niobate, magnesium, and aluminum. Solid solution, dawsonite, and the like.

<Colored curable resin composition>

The dye-dissolving solution (A1) can be used as a dye, and in particular, can be used as a coloring agent for a colored curable resin composition used in a color filter of a display device such as a liquid crystal display.

The content of the xanthene dye (a) in the dye-dissolving liquid (A1) contained in the colored curable resin composition of the color filter is preferably 0.025 based on the total amount of the solid content of the colored curable resin composition. The mass% or more is 48% by mass or less, more preferably 0.08% by mass or more and 42% by mass or less, and further preferably 0.1% by mass or more and 30% by mass or less.

In the present specification, the "total amount of solid content" means the total amount of the components obtained by removing the solvent (E) from the colored curable resin composition of the present invention. The total amount of the solid components and the content of each component with respect to the solid components can be measured, for example, by a known analytical means such as liquid chromatography or gas chromatography.

The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator. Agent (D).

The colorant (A) preferably contains a pigment (P) in addition to the dye solution (A1). Further, a dye (A2) different from the xanthene dye (a) contained in the dye solution (A1) may be contained.

The content of the xanthene dye (a) in the coloring agent (A) is preferably 0.01% by mass or more and 90% by mass or less, and more preferably 0.1% by mass or more and 80% by mass or less based on the total amount of the coloring agent (A).

<Pigment (P)>

The pigment (P) is not particularly limited, and a known pigment can be used. For example, a compound classified as a pigment in a color index (published by The Society of Dyers and Colourists) can be cited.

Examples of the pigment include CI Pigment Yellow 1 (hereinafter, the description of CI Pigment Yellow is omitted, and only the serial number is described), 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, Yellow pigments such as 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; CI Pigment Orange 13, 31, Orange pigments such as 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, Red pigments such as 175, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; CI Pigment Blue 15, 15:3, 15:4, 15:6, 60, 80 color cyan pigment; CI pigment purple 1,19,23,29,32,36,38 and other purple pigments; C.I. Pigment green 7,36,58 and other green pigments; C.I. Pigment brown 23, 25 and other brown pigments; C.I. Pigment black 1, 7 and other black pigments.

These pigments may be used singly or in combination of two or more.

As the pigment, a yellow pigment such as CI Pigment Yellow 138, 139, 150, a red pigment such as CI Pigment Red 177, 242, 254, a Cyan Blue 15, 15:3, 15:4, 15:6, 60, etc. a purple pigment such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38, etc., more preferably at least one selected from the group consisting of CI Pigment Blue 15, 15:3, 15:4, 15:6, and Pigment Violet 23, More preferably, it is at least one selected from the group consisting of CI Pigment Blue 15:6 and Pigment Violet 23. By including the pigment described above, the optimization of the transmission spectrum of the color filter using the color-curable resin composition of the present invention is easy, and the heat resistance, light resistance, and chemical resistance of the color filter are improved.

The colored curable resin composition of the present invention preferably contains a cyan pigment.

For the pigment, if necessary, rosin treatment, surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, graft treatment on a pigment surface using a polymer compound, or the like, and sulfuric acid micronization may be used. A micronization process such as a method, or an organic solvent for removing impurities, a cleaning treatment such as water, or a removal treatment using an ion exchange method or the like for ionic impurities. Preferably, the particle sizes of the pigments are each uniform.

As the above pigment, a pigment dispersion liquid in which a pigment is uniformly dispersed in a solvent can be used.

The pigment dispersion can be obtained by dispersing the pigment and the pigment in a solvent Mixed to get.

In the above mixing, when two or more kinds of pigments are mixed, they may be individually mixed or a plurality of types may be mixed.

The pigment dispersing agent may be a dispersing agent of any of a cationic type, an anionic type, a nonionic type, and an amphoteric type, and examples thereof include a polyester-based, polyamine-based, and acrylic-based pigment dispersant.

These pigment dispersants may be used singly or in combination of two or more. In the case of the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLORENE (manufactured by Kyoeisha Chemical Co., Ltd.), SOLSPERS ( Manufactured by EFKA (manufactured by BASF Corporation), AJISPUR (Ajinomoto) (manufactured by the company), Disperbyk (manufactured by BYK Chemical Co., Ltd.), and the like.

The solvent is not particularly limited, and examples thereof include the same solvents as those in the colored curable resin composition of the present invention.

In the case of using a pigment dispersant, the amount thereof is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the pigment. If the amount of the pigment dispersant used is within the above range, there is a tendency to obtain a pigment dispersion liquid in which a pigment is uniformly dispersed in a solvent.

<dye (A2)>

Examples of the dye (A2) include dyes such as oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes, and examples thereof include color index ( Classified by the Society of Dyers and Colourists) A known dye described in the compound and dyeing note (color dyeing company). Further, examples of the chemical structure include an azo dye, a cyanine dye, a triphenylmethane dye, a xanthene dye, a phthalocyanine dye, a naphthoquinone dye, a quinone imine dye, a methine dye, an azomethine dye, Squaric acid dye, acridine dye, styryl dye, coumarin dye, quinoline dye and nitro dye. Among these, an organic solvent-soluble dye is preferably used.

Specifically, CI solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; CI solvent red 45, 49, 125, 130, 218; CI solvent orange 2, 7, 11, 15, 26, 56; CI solvent blue 4, 5, 37, 67, 70, 90; CI solvent green 1, 4, 5, 7, 34, 35 and other CI solvent dye; CI 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; CI Acid Red 1 , 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91, 92, 94 , 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228 249 252 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107 , 108, 169, 173; CI Acid Violet 6B, 7, 9, 17, 19, 30, 102; CI Acid Blue 1, 7, 9, 15, 18, 22, 29, 42, 59, 60, 62, 70 , 72, 74, 82, 83, 86, 87, 90, 92, 93, 100, 102, 103, 104, 113, 117, 120, 126, 130, 131, 142, 147, 151, 154, 158, 161 , 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335; CI Acid Green 1, CI acid dyes such as 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109; CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50 , 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; CI Direct Red 79, 82, 83, 84, 91, 92, 96, 9 7,98,99,105,106,107,172,173,176,177,179,181,182,184,204,207,211,213,218,220,221,222,232,233,234, 241, 243, 246, 250; CI direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI Direct Blue 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CI direct green CI, 25, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other CI direct dye; CI dispersion yellow 54, 76 and other CI dispersion Dye; CI basic red 1, 10; CI basic blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67 , 68; CI alkaline green 1 and other CI basic dyes; CI active yellow 2, 76, 116; CI active orange 16; CI active red 36 and other CI reactive dyes; CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI mordant red 1, 2, 4, 9, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32 , 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; CI mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI mordant purple 1, 2, 4, 5 , 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; CI mordant blue 1, 2, 3, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61, 74, 77, 83, 84; CI mord green 1, 3, 4 CI mordant dyes such as 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, and 53; CI reduced green 1 and other CI vat dyes.

Among them, a cyan dye, a violet dye, and a red dye are preferred.

These dyes can be appropriately selected depending on the spectroscopic spectrum of the desired color filter. These dyes may be used singly or in combination of two or more.

The content of the colorant (A) is preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50%, based on the total amount of the solid content. Below mass%. When the content of the colorant (A) is within the above range, desired spectral and color concentrations can be obtained.

<Resin (B)>

The resin (B) is not particularly limited, and is preferably an alkali-soluble resin (B). The alkali-soluble resin (B) (hereinafter sometimes referred to as "resin (B)")) is a copolymer containing a structural unit derived from at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride.

Examples of such a resin (B) include the following resins [K1] to [K6].

Resin [K1]: has a structural unit derived from at least one monomer (a) selected from an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (hereinafter sometimes referred to as "(a)"), and has a carbon number of 2~ a copolymer of a cyclic ether structure of 4 and a structural unit of a monomer (b) of an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)"); Resin [K2]: having a structural unit derived from (a) and a structural unit derived from (b), and a monomer (c) from copolymerizable with (a) (however, unlike (a) and (b).) a copolymer of structural units (hereinafter sometimes referred to as "(c)"); Resin [K3]: a copolymer having a structural unit derived from (a) and a structural unit derived from (c); Resin [K4]: a copolymer having a structural unit which adds (b) to a structural unit derived from (a) and a structural unit derived from (c); Resin [K5]: a copolymer having a structural unit which adds (a) to the structural unit derived from (b) and a structural unit derived from (c); Resin [K6]: a copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b), further adding a carboxylic anhydride, and a structural unit derived from (c).

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid; maleic acid, fumaric acid, citraconic acid, and the like. Zhongkang acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-four An unsaturated dicarboxylic acid such as hydrogen phthalic acid, dimethyltetrahydrophthalic acid or 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 - alkene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-B a bicyclic unsaturated compound containing a carboxyl group such as a bicyclo[2.2.1]hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinyl phthalic acid Dicarboxylic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6 -Unsaturated dicarboxylic acid such as dicarboxybicyclo[2.2.1]hept-2-ene anhydride a polyvalent carboxylic acid such as succinic acid mono [2-(methyl) propylene methoxyethyl] ester or phthalic acid mono [2-(methyl) propylene oxyethyl] ester; Unsaturated mono[(meth)acryloxyalkyl]ester; unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule such as α-(hydroxymethyl)acrylic acid.

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

Examples of (b) include 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 group. A polymerizable compound of a bond.

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

In the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth)acrylinyl" and "(meth)acrylate" have the same meaning.

Examples of (b) include a monomer (b1) having an epoxyethyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), having an oxetanyl group and an ethylenically unsaturated bond. The monomer (b2) (hereinafter sometimes referred to as "(b2)"), the monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)")).

(b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)")), A monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-2)").

Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and glycidyl vinyl ether. , o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-Methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl Glycidyl ether, 2,3-bis(glycidoxymethyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl) Styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris(glycidoxymethyl)styrene, 2,3,5-tris(glycidoxy) Methyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris(glycidoxymethyl)styrene, 2,4,6-tri ( Glycidoxymethyl)styrene and the like.

(b1-2), vinyl cyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by Daicel), (meth) 3,4-epoxycyclohexylmethyl acrylate (for example, CYCLOMER A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, CYCLOMER M100;璐 produced), a compound represented by the formula (II), a compound represented by the formula (III), and the like.

In the formulae (II) and (III), R ^a and R ^{b each} represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X ^a and X ^b represents a single ^{bond, * - R c -, *} - R c -O -, * - R c -S- or * -R ^c -NH-.

R ^c represents an alkylene group having 1 to 6 carbon atoms.

* indicates the bonding end with O. ]

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

Examples of the alkyl group in which the hydrogen atom is substituted by 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, and a 1-hydroxy group. Hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

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

Examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, and a butane-1,4-diyl group. Pentane-1,5-diyl, hexane-1,6-diyl and the like.

Preferred examples of X ^a and X ^b include a single bond, a methylene group, an ethylene group, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, and more preferably a single bond, *-CH ₂ CH ₂ -O- (* indicates the bonding end with O).

The compound represented by the formula (II) includes a compound represented by any one of the formulae (II-1) to (II-15). Among them, it is preferred that the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II-9) or the formula (II-11) to the formula (II- The compound represented by 15) is more preferably a compound represented by the formula (II-1), the formula (II-7), the formula (II-9) or the formula (II-15).

The compound represented by the formula (III) may, for example, be a compound represented by any one of the formulae (III-1) to (III-15). Among them, it is preferred that the formula (III-1), the formula (III-3), the formula (III-5), the formula (III-7), the formula (III-9) or the formula (III-11) to the formula (III- The compound represented by 15) is more preferably a compound represented by the formula (III-1), the formula (III-7), the formula (III-9) or the formula (III-15).

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

As (b2), a monomer having an oxetanyl group and a (meth) acryloxy group is more preferable. Examples of (b2) include 3-methyl-3-methylpropenyloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, and 3-ethyl b. 3-methylpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-methylpropenyloxy Ethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methylpropenyloxyethyloxetane, 3- Ethyl-3-propenyloxyethyloxetane and the like.

As (b3), a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, VISCOAT V #150, manufactured by Osaka Organic Chemical Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

(b) is preferably (b1) from the viewpoint of further improving the reliability of heat resistance and chemical resistance of the obtained color filter. Furthermore, (b1-2) is more preferable in that the storage stability of the colored curable resin composition is excellent.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, and t-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, tricyclo [5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate (in the technical field) As a conventional name, it is called "dicyclopentanyl (meth) acrylate." In addition, it is sometimes called "tricyclodecyl (meth) acrylate".), tricyclo(meth) acrylate [5.2.1.0 ^{2 , 6} ]nonene-8-yl ester (in the technical field, as a conventional name, it is called "dicyclopentenyl (meth) acrylate"), (di) pentyloxyethyl (meth) acrylate, (a) Isobornyl acrylate, adamantyl (meth) acrylate, aryl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, (meth) acrylates such as benzyl (meth) acrylate; a hydroxyl group-containing (meth) acrylate such as 2-hydroxyethyl acrylate or 2-hydroxypropyl (meth) acrylate; diethyl maleate, diethyl fumarate, and itaconic acid Dicarboxylic acid diesters such as esters; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2- Alkene, 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]g 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-phenoxy Alkylcarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, a bicyclic unsaturated compound such as 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenylmaleimide, N-cyclohexylmaleimine, N-benzylmaleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4-maleimide butyrate, N - amber quinone imine-6-maleimide caproate, N-amber succinimide-3-maleimide propionate, N-(9-acridinyl) malayan Dicarbonylimine derivatives such as amines; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, A Acrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3- Butadiene, etc.

Among these, from the viewpoints of copolymerization reactivity and heat resistance, styrene, vinyl toluene, benzyl (meth)acrylate, and tricyclo(methyl)acrylate [5.2.1.0 ^2,6 ]decane-8- are preferable. Base ester, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene.

In the resin [K1], the ratio of the structural unit derived from each monomer is preferably a structural unit derived from (a) in all the structural units constituting the resin [K1]: 2 to 60 mol% of the structural unit derived from (b) 40 to 98 mol%, more preferably structural unit derived from (a): 10 to 50 mol% of structural unit derived from (b): 50 to 90 mol%.

If the ratio of the structural unit in the resin [K1] is within the above range, The storage stability of the colored curable resin composition, the developability at the time of forming a colored pattern, and the solvent resistance of the obtained color filter tend to be excellent.

Resin [K1] can be referred to the method described in the "Experimental Method for Polymer Synthesis" (Otsu Takamori Publishing Co., Ltd., the first edition of Chemicals, the first edition, issued on March 1, 1972). The cited literature is manufactured.

Specific examples of the method for producing the resin [K1] include a method in which a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are charged into a reaction vessel, and oxygen is replaced with nitrogen to form a deoxidation. The atmosphere is heated and kept warm while stirring.

In addition, the polymerization initiator, the solvent, and the like used herein are not particularly limited, and those generally used in the field can be used. Examples of the polymerization initiator include an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), and an organic peroxide ( The solvent (E) which is a solvent (E) which is a coloring-curable resin composition of this invention is mentioned later as a solvent, and the solvent etc. are mentioned later.

In addition, as for the obtained copolymer, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used, or a product obtained by reprecipitation or the like as a solid (powder) may be used. In particular, in the polymerization, the solution after the reaction can be used as it is in the preparation of the colored curable resin composition of the present invention by using the solvent contained in the colored curable resin composition of the present invention as a solvent. Therefore, the manufacturing process of the color-curable resin composition of the present invention can be simplified.

In the resin [K2], the ratio of the structural unit derived from each monomer, among all the structural units constituting the resin [K2], is preferably: structural unit derived from (a): 2 to 45 mol% of the structure derived from (b) Unit: 2 to 95 mol% of the structural unit derived from (c): 1 to 65 mol%, more preferably: structural unit derived from (a): 5 to 40 mol% of structural unit derived from (b): 5 to 80 mol % structural unit derived from (c): 5 to 60 mol%.

When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the colored curable resin composition, the developability when a colored pattern is formed, and the solvent resistance and heat resistance of the obtained color filter and The tendency to have excellent mechanical strength.

The resin [K2] can be produced in the same manner as the method described in the production method of the resin [K1], except that a predetermined amount of (c) is further used.

In the resin [K3], the ratio of the structural unit derived from each monomer, among all the structural units constituting the resin [K3], is preferably: structural unit derived from (a): 2 to 60 mol% of the structure derived from (c) Unit: 40 to 98 mol%, more preferably: structural unit derived from (a): 10 to 50 mol% of structural unit derived from (c): 50 to 90 mol%.

The resin [K3] can be produced in the same manner as the method described in the production method of the resin [K1], except that (c) is used instead of (b).

The resin [K4] can be produced by obtaining a copolymer of (a) and (c), adding (b) a cyclic ether having 2 to 4 carbon atoms, and (a) a carboxylic acid and/or a carboxylic anhydride. .

First, the copolymers (a) and (c) can be produced in the same manner as the method described in the production method of the resin [K1]. In this case, the ratio of the structural unit derived from each monomer is preferably the same ratio as the ratio enumerated in the resin [K3].

Next, the cyclic ether having 2 to 4 carbon atoms which is contained in (b) is reacted with a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the above copolymer.

Next, in the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with nitrogen by air, and a catalyst for reacting (b), a carboxylic acid or a carboxylic anhydride with a cyclic ether (for example, tris(dimethylamino) A methyl group of phenol or the like and a polymerization inhibitor (for example, hydroquinone) are placed in a flask, and for example, at 60 to 130 ° C for 1 to 10 hours, the resin [K4] can be produced.

The amount of (b) used is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). When it is in this range, the storage stability of the colored curable resin composition, the developability at the time of pattern formation, and the solvent resistance, heat resistance, mechanical strength, and sensitivity balance of the obtained pattern tend to be good. Since the reactivity of the cyclic ether is high and the unreacted (b) is not easily retained, it is preferably (b1), more preferably (b1-1), as the (b) used for the resin [K4].

The amount of the above reaction catalyst used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c). The amount of the above polymerization inhibitor used relative to 100 parts by mass of the total amount of (a), (b), and (c) It is preferably 0.001 to 5 parts by mass.

The reaction conditions such as the feeding method, the reaction temperature, and the time can be appropriately adjusted in consideration of the production equipment, the amount of heat generation by polymerization, and the like. In addition, similarly to the polymerization conditions, the feeding method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generation by polymerization, and the like.

As the resin [K5], as a first step, a copolymer of (b) and (c) was obtained in the same manner as in the above-described method for producing the resin [K1]. In the same manner as described above, the obtained copolymer may be used as it is, or a concentrated or diluted solution may be used, or a product obtained by reprecipitation or the like as a solid (powder) may be used.

The ratio of the structural unit derived from (b) and (c) is preferably each from the structural unit of (b) with respect to the total number of moles of all the structural units constituting the above copolymer: 5 to 95 mol% from (c) The structural unit: 5 to 95 mol%, more preferably the structural unit derived from (b): 10 to 90 mol% of the structural unit derived from (c): 10 to 90 mol%.

Further, under the same conditions as in the method for producing the resin [K4], the carboxylic acid or carboxylic anhydride having (a) and the cyclic ether of (b) having a copolymer of (b) and (c) are reacted. Thus, the resin [K5] can be obtained.

The amount of (a) to be reacted with the above copolymer is preferably 5 to 80 moles per 100 moles of (b). Since the reactivity of the cyclic ether is high and the unreacted (b) is not easily retained, it is preferably used as the (b) for the resin [K5]. (b1), more preferably (b1-1).

The resin [K6] is a resin obtained by further reacting a carboxylic acid anhydride with a resin [K5]. The carboxylic anhydride is reacted with a hydroxyl group produced by the reaction of a cyclic ether with a carboxylic acid or a carboxylic anhydride.

Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, and 3,4,5,6-tetrahydroortylene. Dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. . The amount of the carboxylic anhydride used is preferably 0.5 to 1 mol based on 1 mol of the amount used in (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer and (meth)acrylic acid 3,4-epoxytricyclo[5.2. .1.0 ^2.6 ]Resin such as oxime ester/(meth)acrylic acid copolymer [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, (meth)acrylic acid glycidyl methacrylate / styrene / (meth) acrylic acid copolymer, (meth) acrylate, 3,4-epoxy-tricyclo [5.2.1.0 ^2.6] decyl acrylate / (meth) acrylic acid / N- acyl-cyclohexylmaleimide Imine copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl (meth)acrylic/vinyltoluene copolymer, 3-methyl-3-(methyl) (meth)acrylate Resin such as acryloxymethyloxetane/(meth)acrylic acid/styrene copolymer [K2]; benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(methyl a resin such as an acrylic copolymer, benzyl (meth)acrylate/tricyclodecyl (meth)acrylate/(meth)acrylic copolymer; [K3]; glycidyl (meth)acrylate and (methyl) a resin obtained by adding benzyl acrylate/(meth)acrylic acid copolymer to make (meth) propylene a resin obtained by adding a glycidyl ester to a tricyclodecyl (meth) acrylate/styrene/(meth)acrylic acid copolymer, a glycidyl (meth)acrylate and a tricyclodecyl (meth)acrylate a resin such as a resin obtained by adding a benzyl (meth) acrylate/(meth)acrylic acid copolymer [K4]; a (meth)acrylic acid and a tricyclodecyl (meth)acrylate/(meth)acrylic acid a resin obtained by reacting a copolymer of glycidyl ester, a resin such as a resin obtained by reacting a copolymer of (meth)acrylic acid and tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate; [K5]; a resin obtained by reacting a copolymer of (meth)acrylic acid with a tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate to further react with tetrahydrophthalic anhydride Resin such as resin [K6].

The resin (B) is preferably one selected from the group consisting of a resin [K1], a resin [K2], and a resin [K3], and more preferably one selected from the group consisting of a resin [K2] and a resin [K3]. When it is these resins, the coloring curable resin composition is excellent in developability. From the viewpoint of the adhesion between the colored pattern and the substrate, the resin [K2] is more preferable.

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, still more preferably 5,000 to 30,000. When the molecular weight is within the above range, the coating film hardness is increased, the residual film ratio is also 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 from 1.1 to 6, more preferably from 1.2 to 4.

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

The content of the resin (B) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, even more preferably from 17 to 55% by mass, based on the total amount of the solid components. 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 residual film ratio tend to be improved.

<Polymerizable compound (C)>

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

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

Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, and neopentyl glycol di(methyl). Acrylate, triethylene glycol di(meth)acrylate, bis(acryloxyethyl)ether of bisphenol A, 3-methylpentyl Glycol di(meth)acrylate or the like.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylic acid. Ester, dipentaerythritol hexa(meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentaerythritol deca (meth) acrylate, pentaerythritol nin (meth) acrylate Ester, tris(2-(meth)acryloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate Ester, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth) acrylate, caprolactone modified pentaerythritol tetra(meth) acrylate, caprolactone modified dipentaerythritol hexa Methyl) acrylate or the like, among which dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

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

The content of the polymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, even more preferably from 15 to 55% by mass, based on the total amount of the solid component.

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

When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of formation of the colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>

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

Examples of the polymerization initiator (D) include an O-indenyl hydrazine compound, an alkyl phenyl ketone compound, a biimidazole compound, a triazine compound, and a fluorenyl phosphine oxide compound.

The above O-indenyl ruthenium compound is a compound having a structure represented by the formula (d1). Hereinafter, * indicates the bonding end.

Examples of the above O-indenyl ruthenium compound include N-benzylideneoxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imide and N-benzoic acid.醯oxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole- 3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4- Dioxolylmethoxy)benzhydryl}-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl-6- (2-methylbenzimidyl)-9H-indazol-3-yl]-3-cyclopentyl Propane-1-imine and N-benzylideneoxy-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-3-ring Amyl propan-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (above, manufactured by BASF Corporation), and N-1919 (made by ADEKA Co., Ltd.) can be used. Wherein the O-indenyl hydrazine compound is preferably selected from the group consisting of N-benzylideneoxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzylformamide 1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-benzylideneoxy-1-(4-phenylsulfanylphenyl)-3 At least one of cyclopentylpropan-1-one-2-imine, more preferably N-benzylideneoxy-1-(4-phenylsulfanylphenyl)octane-1-one- 2-imine. If it is these O-fluorenyl hydrazine compounds, it tends to obtain a high-density color filter.

The above alkyl phenyl ketone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In these partial structures, the benzene ring may have a substituent.

The compound having a structure represented by the formula (d2) includes 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethyl Amino-1-(4-morpholinophenyl)-2-benzylbutan-1-one and 2-(dimethylamino)-2-[(4-methylphenyl)methyl ]-1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. Commercial products such as Irgacure 369, 907, and 379 (above, manufactured by BASF Corporation) can be used.

As a compound having a structure represented by the formula (d3), a 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, Oligomer of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone And benzoin dimethyl ketal and the like.

From the viewpoint of sensitivity, the alkyl phenyl ketone compound is preferably a compound having a structure represented by the formula (d2).

The biimidazole compound may, for example, be a compound represented by the formula (d5).

In the formula (d5), R ¹³ to R ¹⁸ 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 include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, and a naphthyl group, and a phenyl group is preferable.

Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably 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.

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, JP-A-6-75373, etc.), 2, 2' - double (2- Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxy) Phenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis (2 -Chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, Japanese Patent Publication No. Sho 48-38403, JP-A-62-174204, etc.) And a biimidazole compound in which a phenyl group at the 4,4', 5, 5'-position is substituted with an alkoxycarbonyl group (for example, see Japanese Patent Laid-Open Publication No. Hei 7-10913, etc.). Among them, preferred are compounds represented by the following formulas and mixtures thereof.

Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-bis (three). Chloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-three Pyrazine, 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-three And so on.

The above fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide.

Further, examples of the polymerization initiator (D) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. a compound; benzophenone, methyl o-benzhydrylbenzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3', a benzophenone compound such as 4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone or 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethyl Anthraquinone compounds such as guanidine and camphor; 10-butyl-2-chloroacridone, benzophenone, methyl phenylglyoxylate, and titanocene compound.

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

The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of an alkyl phenyl ketone compound, a triazine compound, a fluorenyl phosphine oxide compound, an O-mercapto fluorene compound, and a biimidazole compound, and more preferably A polymerization initiator comprising an O-indenyl ruthenium compound.

The content of the polymerization initiator (D) is preferably 0.01 to 40 parts by mass, more preferably 0.05 to 35 parts by mass, even more preferably 0.1% by mass based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). ~32 parts by mass, particularly preferably 1 to 30 parts by mass.

<Polymerization Initiator (D1)>

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

As the polymerization initiation aid (D1), an amine compound, an alkoxy group is exemplified. A base compound, a thioxanthone compound, a carboxylic acid compound, and the like.

The amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate or 4-dimethyl Isoamyl benzoate benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4, 4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone and 4,4'-bis (ethyl group) The amino group) benzophenone or the like is preferably, for example, 4,4'-bis(diethylamino)benzophenone. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

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

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

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, and dimethylphenyl. Sulfoalkylacetate, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine , phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthyloxyacetic acid, and the like.

In the case of using these polymerization initiating aids (D1), The content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). If the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to increase.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent which is generally used in the field can be used. For example, an ester solvent (a solvent containing -COO- or a solvent containing no -O- in a molecule), an ether solvent (a solvent containing -O- in the molecule, a solvent containing no -COO-), an ether ester solvent (in the molecule) a solvent containing -COO- and -O-), a ketone solvent (a solvent containing -CO- in the molecule, a solvent not containing -COO-), an alcohol solvent (containing OH in the molecule, and containing no -O-, -CO) - and -COO-solvent), aromatic hydrocarbon solvent, guanamine solvent, and dimethyl hydrazine.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, and isoamyl acetate. , butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, ring Hexanol 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, and 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, tetrahydrogen Pyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl Ether, anisole, phenethyl ether and methyl anisole.

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

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

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

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and 1,3,5-trimethylbenzene.

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

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

Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and digan are preferred. Alcohol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc., more preferably propylene glycol monomethyl ether acetate, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monomethyl ether, B Glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 3-methoxypropionic acid Ester, ethyl 3-ethoxypropionate and N-methylpyrrolidone.

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

<Leveling agent (H)>

Examples of the leveling agent (H) include an organic lanthanoid surfactant, a fluorine-based surfactant, and an organic lanthanoid surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the organic oxime-based surfactant include surfactants having a decane bond in the molecule. Specifically, TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: Toray-Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 ( ‧ ‧ ‧ Contract company made) and so on.

The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain in the molecule. Specifically, it can be enumerated (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), (registered trademark) S381, S382, SC101, SC105 (made by Asahi Glass Co., Ltd.) and E5844 (( ) Research institute manufacturing).

The organic ruthenium-based surfactant having a fluorine atom as described above includes a surfactant having a siloxane chain and a fluorocarbon chain in the molecule. Specifically, it can be enumerated (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

When the leveling agent (H) is contained, the content thereof is preferably 0.001% by mass or more and 0.2% by mass or less, and more preferably 0.002% by mass or more and 0.1% by mass or less based on the total amount of the colored curable resin composition. More preferably, it is 0.005 mass % or more and 0.07 mass % or less. If leveling When the content of the agent (H) is within the above range, the flatness of the color filter can be improved.

<Antioxidant (J)>

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

Examples of the phenolic antioxidant include 1010 (Irganox 1010: pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Co., Ltd.) 1076 (Irganox 1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by BASF Corporation), 1330(Irganox 1330:3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mestrimethylbenzene-2,4,6-three Base) tri-p-cresol, manufactured by BASF Co., Ltd., 3114 (Irganox 3114: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H, 5H)-trione, manufactured by BASF Co., Ltd., 3790 (Irganox 3790: 1,3,5-tris((4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl)-1,3,5-triazine-2,4, 6(1H,3H,5H)-trione, manufactured by BASF Co., Ltd., 1035 (Irganox 1035: thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Corporation), 1135 (Irganox 1135: phenylpropionic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxyl, C7-C9 side chain alkyl ester, manufactured by BASF Corporation), 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF Co., Ltd.), 3125 (Irganox 3125, manufactured by BASF Corporation), 565 (Irganox 565: 2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butylanilino)-1,3,5-triazine, BASF Co., Ltd.) AO-80( AO-80: 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy)-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro(5,5)undecane, manufactured by ADEKA, BHT (Sumilizer BHT, manufactured by Sumitomo Chemical Co., Ltd.), GA-80 (Sumilizer GA-80, manufactured by Sumitomo Chemical Co., Ltd.), GS (Sumilizer GS, manufactured by Sumitomo Chemical Co., Ltd.), 1790 (Cyanox 1790, Ltd.) Manufacture) and vitamin E ( (manufactured by the company) and so on.

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

Examples of the sulfur-based antioxidant include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl or distearyl, and tetrakis [methylene (3- A ?-alkylmercaptopropionate compound of a polyhydric alcohol such as dodecylthio)propionate].

<Other ingredients>

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

<Method for Producing Colored Curable Resin Composition>

The colored curable resin composition 0 of the present invention can be used by using a dye dissolving solution (A1), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), and if necessary. Prepared by mixing a leveling agent (H), a polymerization initiation aid (D1), an antioxidant (J), and other ingredients.

The colored curable resin composition 1 of the present invention can be obtained by dissolving a dye solution (A1), a dye (A2), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E). And, if necessary, a leveling agent (H), a polymerization initiation aid (D1), an antioxidant (J), and other components are mixed and prepared.

The colored curable resin composition 2 of the present invention can be obtained by dissolving a dye solution (A1), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a colorless metal complex (F), and The solvent (E) and, if necessary, a leveling agent (H), a polymerization initiation aid (D1), an antioxidant (J), and other components are prepared and mixed.

In the case where the pigment (P) is contained, the pigment is preferably mixed with a part or all of the solvent (E) in advance, and dispersed by a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. In this case, a part or all of the above-mentioned pigment dispersant and resin (B) may be blended as needed. By mixing the remaining components in the pigment dispersion liquid thus obtained to have a predetermined concentration, the intended colored curable resin composition can be prepared.

The colorant (A) such as the dye solution (A1) or the dye (A2) is preferably dissolved in a part or all of the solvent (E) to prepare a solution. It is preferred to filter the solution with a filter having a pore diameter of about 0.01 to 1 μm.

The mixed colored curable resin composition is preferably filtered by a filter having a pore diameter of about 0.01 to 10 μm.

<Method of Manufacturing Color Filter>

A method of producing a colored pattern by the colored curable resin composition of the present invention includes a photolithography method, an inkjet method, a printing method, and the like, and a photolithography method is preferable. In the photolithography method, the colored curable resin composition is applied onto a substrate, dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. In the photolithography method, a coloring coating film which is a cured product of the coloring composition layer can be formed by using a photomask and/or no development at the time of exposure. The colored pattern thus formed The color coating film is the color filter of the present invention.

The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted depending on the purpose, use, and the like, and is usually 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, quartz glass, borosilicate glass, aluminosilicate glass, a glass plate such as soda lime glass coated with cerium oxide on the surface, polycarbonate, polymethyl methacrylate, and polyparaphenyl may be used. A resin plate such as ethylene glycol diester or the like, and a product such as an aluminum, silver, silver/copper/palladium alloy thin film formed on the substrate. Additional color filter layers, resin layers, transistors, circuits, and the like can be formed on these substrates.

The formation of each color pixel by photolithography can be carried out under known or conventional devices and conditions. For example, it can be produced as follows.

First, the colored curable resin composition is applied onto a substrate, and dried by heating (prebaking) and/or drying under reduced pressure to remove a volatile component such as a solvent and dry it to obtain a smooth colored composition layer.

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

The temperature at the time of heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. Further, the heating time is preferably from 10 seconds to 60 minutes, and more preferably from 30 seconds to 30 minutes.

In the case of drying under reduced pressure, it is preferably carried out under a pressure of 50 to 150 Pa at a temperature of 20 to 25 °C.

The film thickness of the coloring composition layer is not particularly limited, and can be appropriately selected depending on the film thickness of the target color filter.

Next, the colored composition layer is exposed through a photomask for forming a colored pattern of the target. The pattern on the photomask is not particularly limited, and a pattern matching the intended use can be used.

As the light source for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, a light having a wavelength of less than 350 nm may be cut off by a filter that cuts the wavelength range, or a light in the vicinity of 436 nm, around 408 nm, and around 365 nm may be selectively taken out by a band pass filter that takes out these wavelength ranges. Specifically, examples of the light source include a mercury lamp, a light-emitting diode, a metal halide lamp, a halogen lamp, and the like.

Since the parallel light rays can be uniformly irradiated to the entire exposed surface, and the correct alignment of the photomask and the substrate on which the colored composition layer is formed is performed, it is preferable to use an exposure apparatus such as a mask aligner and a stepper.

The colored composition layer after exposure is developed in contact with the developer to form a colored pattern on the substrate. By development, the unexposed portion of the colored composition layer is dissolved in the developer to be removed. As the developer, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferable. The concentration in the aqueous solution of these basic compounds is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.

The developing method may be any one of a spin coating immersion method, a dipping method, and a spray method. Further, the substrate can be inclined at an arbitrary angle during development.

It is preferred to carry out water washing after development.

Further, it is preferred to post-bait the obtained colored pattern. As the post-baking temperature, it is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. Post-baking The baking time is preferably from 1 to 120 minutes, more preferably from 10 to 60 minutes.

By using the colored curable resin composition of the present invention, a color filter having particularly high brightness can be produced. This color filter can be used as a color filter for a display device (for example, a liquid crystal display device, an organic EL device, an electronic paper, or the like) and a solid-state image pickup element.

Example

The present invention will be more specifically described by the following examples, but the present invention is not limited by the following examples at all, and it is of course possible to carry out the appropriate changes within the scope of the main contents which can be described later. They are all included in the technical scope of the present invention. Incidentally, hereinafter, "parts" means "parts by mass" and "%" means "mass%" unless otherwise specified.

The present invention will be specifically described below based on the examples, but the present invention is not limited by these examples. In the examples, the content and the % and the amount of the use amount are shown as the mass basis unless otherwise specified.

[Example 1]

Propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA. manufactured by Daicel) / diacetone was added to 25 parts of lithium bis(trifluoromethanesulfonyl)imide (manufactured by Tokyo Chemical Industry Co., Ltd.). Alcohol (hereinafter abbreviated as DAA. KH 450 parts of a mixed solvent (hereinafter abbreviated as mixed solvent A) of 10/90 (weight ratio) was stirred at room temperature for 10 minutes to complete dissolution. 25 parts of the compound represented by the formula (I-1) was added, and the mixture was further stirred at room temperature for 13 hours. To the obtained solution, 3.2 parts of Celite 535 (manufactured by Izumi Pure Chemical Industries, Ltd.) was added, and the mixture was further stirred at room temperature for 1 hour. The obtained solution was filtered through Tongshan filter paper No. 5C. The obtained filtrate was further passed through a PTFE membrane disc filter PTAW04700 (1 μm) and S4422 M022Y11 (0.05 μm) under a pressure of 0.05 MPa of nitrogen (Japan) Filtration was carried out, and 470.0 parts of a dye solution (A1-1) was obtained.

[Embodiment 2]

450 parts of the mixed solvent A was added to 25 parts of lithium bis(trifluoromethanesulfonyl)imide (manufactured by Tokyo Chemical Industry Co., Ltd.), and the mixture was stirred at room temperature for 10 minutes to complete dissolution. 25 parts of the compound represented by the formula (I-119) was added, and the mixture was further stirred at room temperature for 13 hours. To the obtained solution, 3.2 parts of Celite 535 (manufactured by Izumi Pure Chemical Industries, Ltd.) was added, and the mixture was further stirred at room temperature for 1 hour. The obtained solution was filtered through Kiriyama filter paper No. 5B, and the obtained solution was further filtered through Kiriyama filter paper No. 5C. The obtained filtrate was further passed through a PTFE membrane disc filter PTAW04700 (1 μm) and S4422 M022Y11 (0.05 μm) under a pressure of 0.05 MPa of nitrogen (Japan) The product was filtered, and 470.0 parts of a dye solution (A1-2) was obtained.

[Example 3]

470 parts of PGMEA (manufactured by Daicel) was added to 5.0 parts of lithium bis(trifluoromethanesulfonyl)imide (manufactured by Tokyo Chemical Industry Co., Ltd.), and the mixture was stirred at room temperature for 10 minutes to complete dissolution. 25 parts of the compound represented by the formula (I-155) was added, and the mixture was further stirred at room temperature for 13 hours. To the obtained solution, 5.3 parts of Celite 535 (manufactured by Izumi Pure Chemical Industries, Ltd.) was added, and the mixture was further stirred at room temperature for 1 hour. The obtained solution was filtered through Tongshan filter paper No. 5C. The obtained filtrate was further passed through an ultrahigh molecular weight polyethylene (UPE) membrane disc filter CWUA04700 (1 μm), CWAZ04700 (0.05 μm) under a pressure of 0.05 MPa of nitrogen (Japan) The product was filtered, and 470.0 parts of a dye solution (A1-3) was obtained.

[Example 4]

450 parts of the mixed solvent A was added to 25 parts of lithium bis(trifluoromethanesulfonyl)imide (manufactured by Tokyo Chemical Industry Co., Ltd.), and the mixture was stirred at room temperature for 10 minutes to complete dissolution. 25 parts of the compound represented by the formula (I-160) was added, and the mixture was further stirred at room temperature for 13 hours. To the obtained solution, 3.2 parts of Celite 535 (manufactured by Izumi Pure Chemical Industries, Ltd.) was added, and the mixture was further stirred at room temperature for 1 hour. The obtained solution was filtered through Tongshan filter paper No. 5C. The obtained filtrate was further passed through a PTFE membrane disc filter PTAW04700 (1 μm) and S4422 M022Y11 (0.05 μm) under a pressure of 0.05 MPa of nitrogen (Japan) The product was filtered, and 470.0 parts of a dye solution (A1-4) was obtained.

[Example 5]

450 parts of the mixed solvent A was added to 25 parts of lithium bis(trifluoromethanesulfonyl)imide (manufactured by Tokyo Chemical Industry Co., Ltd.), and the mixture was stirred at room temperature for 10 minutes to complete dissolution. 25 parts of the compound represented by the formula (I-161) was added, and the mixture was further stirred at room temperature for 13 hours. To the obtained solution, 3.2 parts of Celite 535 (manufactured by Izumi Pure Chemical Industries, Ltd.) was added, and the mixture was further stirred at room temperature for 1 hour. The obtained solution was filtered through Tongshan filter paper No. 5C. The obtained filtrate was further passed through a PTFE membrane disc filter PTAW04700 (1 μm) and S4422 M022Y11 (0.05 μm) under a pressure of 0.05 MPa of nitrogen (Japan) The product was filtered, and 470.0 parts of a dye solution (A1-5) was obtained.

[Embodiment 6]

44 parts of the mixed solvent A was added to 25 parts of the compound represented by the formula (I-1), and the mixture was stirred at room temperature for 30 minutes to complete dissolution. To the obtained solution, 25 parts of 3-methylpropenyloxypropyltrimethoxydecane (KBM-503: manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the mixture was further stirred at room temperature for 15 hours. To the obtained solution, 5.3 parts of Celite 535 (manufactured by Izumi Pure Chemical Industries, Ltd.) was added, and the mixture was further stirred at room temperature for 1 hour. The obtained solution was filtered through Kiriyama filter paper No. 5B, and the obtained filtrate was further filtered through Kiriyama filter paper No. 5C. The obtained filtrate was further passed through a PTFE membrane disc filter PTAW04700 (1 μm) and S4422 M022Y11 (0.05 μm) under a pressure of 0.05 MPa of nitrogen (Japan) (manufactured by the company) was filtered to obtain 485 parts of the dye solution (A1-6).

[Embodiment 7]

470 parts of PGMEA (manufactured by Daicel) was added to 5.0 parts of lithium tris(trifluoromethanesulfonyl) methide (manufactured by Toyo Co., Ltd.), and the mixture was stirred at room temperature for 10 minutes to complete dissolution. 25 parts of the compound represented by the formula (I-155) was added, and the mixture was further stirred at room temperature for 13 hours. Add in the obtained solution 5.3 parts of 700 SEN-S (manufactured by Kyowa Chemical Industry Co., Ltd.), and further stirred at room temperature for 1 hour. The obtained solution was filtered through Tongshan filter paper No. 5C. The obtained filtrate was further passed through an ultrahigh molecular weight polyethylene (UPE) membrane disc filter CWUA04700 (1 μm), CWAZ04700 (0.05 μm) under a pressure of 0.05 MPa of nitrogen (Japan) The product was filtered, and 470.0 parts of a dye solution (A1-7) was obtained.

[Embodiment 8]

450 parts of the mixed solvent A was added to 25 parts of lithium bis(trifluoromethanesulfonyl)imide (manufactured by Tokyo Chemical Industry Co., Ltd.), and the mixture was stirred at room temperature for 10 minutes to complete dissolution. 25 parts of the compound represented by the formula (I-161) was added, and the mixture was further stirred at room temperature for 13 hours. Add in the obtained solution 3.2 parts (manufactured by Kyowa Chemical Industry Co., Ltd.) was further stirred at room temperature for 1 hour. The obtained solution was filtered through Tongshan filter paper No. 5C. The obtained filtrate was further passed through a PTFE membrane disc filter PTAW04700 (1 μm) and S4422 M022Y11 (0.05 μm) under a pressure of 0.05 MPa of nitrogen (Japan) The product was filtered, and 470.0 parts of a dye solution (A1-8) was obtained.

[Embodiment 9]

450 parts of the mixed solvent A was added to 25 parts of lithium bis(trifluoromethanesulfonyl)imide (manufactured by Tokyo Chemical Industry Co., Ltd.), and the mixture was stirred at room temperature for 10 minutes to complete dissolution. 25 parts of the compound represented by the formula (I-1) was added, and the mixture was further stirred at room temperature for 13 hours. Add in the obtained solution 3.2 parts of 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was further stirred at room temperature for 1 hour. The obtained solution was filtered through Tongshan filter paper No. 5C. The obtained filtrate was further passed through a PTFE membrane disc filter PTAW04700 (1 μm) and S4422 M022Y11 (0.05 μm) under a pressure of 0.05 MPa of nitrogen (Japan) Filtration was carried out, and 470.0 parts of a dye solution (A1-9) was obtained.

[Embodiment 10]

445.7 parts of the mixed solvent A was added to 25 parts of the compound represented by the formula (I-1), and the mixture was stirred at room temperature for 30 minutes to complete dissolution. To the obtained solution, 25 parts of 3-methylpropenyloxypropyltrimethoxydecane (KBM-503: manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the mixture was further stirred at room temperature for 15 hours. Add in the obtained solution 5.3 parts of 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was further stirred at room temperature for 1 hour. The obtained solution was filtered through Kiriyama filter paper No. 5B, and the obtained filtrate was further filtered through Kiriyama filter paper No. 5C. The obtained filtrate was further passed through a PTFE membrane disc filter PTAW04700 (1 μm) and S4422 M022Y11 (0.05 μm) under a pressure of 0.05 MPa of nitrogen (Japan) (manufactured by the company) was filtered to obtain 485 parts of the dye solution (A1-10).

[Example 11]

Zinc bis(3,5-di-tert-butylsalicylate) (BONTRON (registered trademark) E-84 ( To the 25 parts, 450 parts of the mixed solvent A was added to 25 parts, and the mixture was stirred at room temperature for 10 minutes to complete dissolution. 25 parts of the compound represented by the formula (I-161) was added, and the mixture was further stirred at room temperature for 13 hours. Add in the obtained solution 3.2 parts (manufactured by Kyowa Chemical Industry Co., Ltd.) was further stirred at room temperature for 1 hour. The obtained solution was filtered through Tongshan filter paper No. 5C. The obtained filtrate was further passed through a PTFE membrane disc filter PTAW04700 (1 μm) and S4422 M022Y11 (0.05 μm) under a pressure of 0.05 MPa of nitrogen (Japan) The product was filtered, and 470.0 parts of a dye solution (A1-11) was obtained.

[Comparative Example 1]

15 parts of the compound represented by the formula (I-155) was added to 485 parts of PGMEA (manufactured by Daicel), and the mixture was stirred at room temperature for 50 hours. The compound represented by the formula (I-155) was not completely dissolved, and the solution was suspended. The obtained solution was filtered through Tongshan filter paper No. 5C, but the weight of the residue after drying was 12 parts, and it was found that the residue was dissolved.

[Comparative Example 2]

25 parts of the compound represented by the formula (I-1) was added to 475 parts of the mixed solvent A, and the mixture was stirred at room temperature for 15 hours, and 5.3 parts of Celite 535 (manufactured by Izumi Pure Chemical Industries, Ltd.) was added thereto, and further at room temperature. Stir for 1 hour. The obtained solution was filtered through Kiriyama filter paper No. 5B, and the obtained solution was further filtered through Kiriyama filter paper No. 5C. The obtained filtrate was further passed through a PTFE membrane disc filter PTAW04700 (1 μm) and S4422 M022Y11 (0.05 μm) under a pressure of 0.05 MPa of nitrogen (Japan) (manufactured by the company) was filtered to obtain 485 parts of the dye solution (A1-R2).

[Comparative Example 3]

25 parts of the compound represented by the formula (I-160) was added to 475 parts of the mixed solvent A, and the mixture was stirred at room temperature for 15 hours, and 5.3 parts of Celite 535 (manufactured by Lin Pure Chemical Industries, Ltd.) was added thereto, and further at room temperature. Stir for 1 hour. The obtained solution was filtered through Tongshan filter paper No. 5C. The obtained filtrate was further passed through a PTFE membrane disc filter PTAW04700 (1 μm) and S4422 M022Y11 (0.05 μm) under a pressure of 0.05 MPa of nitrogen (Japan) The product was filtered, and 485 parts of a dye solution (A1-R3) was obtained.

[Comparative Example 4]

25 parts of the compound represented by the formula (I-161) was added to 475 parts of the mixed solvent A, and the mixture was stirred at room temperature for 15 hours, and 5.3 parts of Celite 535 (manufactured by Link Pure Chemical Industries, Ltd.) was added thereto, and further at room temperature. Stir for 1 hour. The obtained solution was filtered through Tongshan filter paper No. 5C. The obtained filtrate was further passed through a PTFE membrane disc filter PTAW04700 (1 μm) and S4422 M022Y11 (0.05 μm) under a pressure of 0.05 MPa of nitrogen (Japan) Filtration of the company was carried out, and 485 parts of the dye solution (A1-R4) was obtained.

[Comparative Example 5]

25 parts of the compound represented by the formula (I-119) were added to 475 parts of the mixed solvent A, and the mixture was stirred at room temperature for 15 hours, and then added to 5.3 parts of Celite 535 (manufactured by Izumi Pure Chemical Industries, Ltd.), and further at room temperature. Stir for 1 hour. The obtained solution was filtered through Kiriyama filter paper No. 5B, and the obtained solution was further filtered through Kiriyama filter paper No. 5C. The obtained filtrate was further passed through a PTFE membrane disc filter PTAW04700 (1 μm) and S4422 M022Y11 (0.05 μm) under a pressure of 0.05 MPa of nitrogen (Japan) Filtration was carried out, and 485 parts of a dye solution (A1-R5) was obtained.

[Comparative Example 6]

25 parts of the compound represented by the formula (I-161) was added to 475 parts of the mixed solvent A, and stirred at room temperature for 15 hours, and added. 5.3 parts (manufactured by Kyowa Chemical Industry Co., Ltd.) was further stirred at room temperature for 1 hour. The obtained solution was filtered through Tongshan filter paper No. 5C. The obtained filtrate was further passed through a PTFE membrane disc filter PTAW04700 (1 μm) and S4422 M022Y11 (0.05 μm) under a pressure of 0.05 MPa of nitrogen (Japan) The product was filtered, and 485 parts of a dye solution (A1-R6) was obtained.

[Comparative Example 7]

25 parts of the compound represented by the formula (I-1) was added to 475 parts of the mixed solvent A, and stirred at room temperature for 15 hours, and added. 5.3 parts of 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was further stirred at room temperature for 1 hour. The obtained solution was filtered through Kiriyama filter paper No. 5B, and the obtained solution was further filtered through Kiriyama filter paper No. 5C. The obtained filtrate was further passed through a PTFE membrane disc filter PTAW04700 (1 μm) and S4422 M022Y11 (0.05 μm) under a pressure of 0.05 MPa of nitrogen (Japan) Filtration of the company was carried out, and 485 parts of the dye solution (A1-R7) was obtained.

<Confirmation of stability over time>

The dye solution obtained in each of Examples 1 to 6 and Comparative Examples 2 to 5 was stored at each of -20 ° C, 10 ° C, 23 ° C, and 40 ° C, and the presence or absence of the precipitate was visually confirmed one week later. The results are shown in Table 1. "○" indicates that no precipitates were confirmed, and "X" indicates that precipitates were confirmed.

Industrial availability

According to the method for producing a dye-dissolving liquid according to the present invention, since a dye-dissolving liquid having excellent stability with time can be produced, it is possible to suppress the formation of precipitates in accordance with the change over time in the obtained dye-dissolving solution. The dye-dissolving liquid having excellent stability over time can be further mixed with the resin (B), the polymerizable compound (C), and the polymerization initiator (D) to form a colored curable resin composition, and the colored curable resin composition is used. The color filter and the display device can be efficiently manufactured.

Claims (10)

A method for producing a dye solution comprising: stirring at least one of (a) xanthene dye, and (b) a salt selected from the group consisting of an organic acid and a compound containing a ruthenium atom in the presence of an organic solvent; Process. The method for producing a dye solution according to claim 1, further comprising a solid-liquid separation step after the stirring step. The method for producing a dye-dissolving solution according to claim 1, wherein the organic acid is selected from the group consisting of an aliphatic carboxylic acid, an aromatic carboxylic acid, an aliphatic sulfonic acid, an alicyclic sulfonic acid, and an aromatic sulfonic acid, At least one of a compound represented by the formula (h1) and a compound represented by the following formula (h2) constitutes the aliphatic carboxylic acid, the aromatic carboxylic acid, the aliphatic sulfonic acid, and the aromatic The hydrogen atom other than the acidic proton of the sulfonic acid may be substituted by a halogen atom or a hydroxyl group, and the -CH ₂ - constituting the aliphatic carboxylic acid, the aliphatic sulfonic acid, and the alicyclic sulfonic acid may be -CO- replace, In the formula (h1), X ^h1 and X ^h2 independently of each other represent a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms, or X ^h1 and X ^{h2 are} combined to form a fluoroalkylene group having 2 to 4 carbon atoms. In the formula (h2), X ^h3 to X ^h5 independently represent a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms. The method for producing a dye-dissolving solution according to claim 1, wherein the compound containing a ruthenium atom is a compound represented by the following formula (j): Rh ² -Si-(R ^h1 ) ₃ (j) Formula (j) In the above, R ^h1 represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and a plurality of ^{Rh 1} may be the same or different, and ^{Rh 2} represents a monovalent substituent. The method for producing a dye-dissolving solution according to claim 1, wherein the organic solvent is a carboxylate of an alkylene glycol monoalkyl ether, an aliphatic alcohol having a ketocarbonyl group, or a mixed solvent thereof. The method for producing a dye solution according to claim 1, wherein the xanthene dye is represented by the following formula (1a): In the formula (1a), R ¹ to R ⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a monovalent aromatic having 6 to 10 carbon atoms which may have a substituent. a hydrocarbon group or a group represented by the formula (ii), *-R ⁵⁰ -Si(R ²⁹ ) ₃ (ii) In the formula (ii), R ²⁹ represents a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms. Or an alkoxy group having 1 to 4 carbon atoms, a plurality of R ²⁹ may be the same or different from each other, R ⁵⁰ represents an alkylene group having 1 to 10 carbon atoms, and -CH ₂ - constituting the alkylene group may be -O- , -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-, but the adjacent -CH ₂ - will not be replaced at the same time The group, the other terminal -CH ₂ - will not be replaced, * represents the bonding end with the nitrogen atom, and in R ¹ to R ⁴ , the -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-, R ¹ and R ² together form a ring containing a nitrogen atom, R ³ and R ⁴ may together form a ring containing a nitrogen atom, however, the adjacent -CH ₂ - is replaced at the same time is not similar groups, additional terminal -CH ₂ - can not be replaced R ⁵ represents ^{_{-OH, -SO 3 -, -SO 3}} H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ NR ⁹ R ¹⁰ , R ⁶ and R ⁷ independently of each other represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m represents an integer of 0 to 5, and when m is 2 or more, plural R ^{5 's} may be the same or different , a represents an integer of 0 or 1, X represents a halogen atom, Z ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and four R ^{11 's} may be the same or different, and R ⁸ represents a carbon number of 1 to 20 a monovalent saturated hydrocarbon group in which a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and R ⁹ and R ¹⁰ independently of each other represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent The -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO- Alternatively, R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered ring heterocyclic ring containing a nitrogen atom, however, the adjacent -CH ₂ - may not be simultaneously substituted with the same group, and the terminal -CH ₂ - R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. The method for producing a dye-dissolving solution according to claim 1, wherein the xanthene dye is a compound represented by the following formula (1d): In the formula (1d), R ^1d to R ^4d independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a monovalent aromatic having 6 to 10 carbon atoms which may have a substituent. a group of a hydrocarbon group or a group represented by the formula (ii), at least one of R ^1d to R ^4d is a group represented by the formula (ii), *-R ⁵⁰ -Si(R ²⁹ ) ₃ (ii) In (ii), R ²⁹ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and a plurality of R ^{29 's} may be the same or different, and R ⁵⁰ represents a carbon number of 1. ~10 alkylene, -CH ₂ - constituting the alkylene group may be -O-, -CO-, -NR ^11d -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH - or -NHCO- substitution, however, the adjacent -CH ₂ - will not be replaced by the same group at the same time, in addition, the terminal -CH ₂ - will not be replaced, * indicates the bonding end with the nitrogen atom, R ^{In 1d} to R ^4d , -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO-, -NR ^11d -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH - Alternatively, or -NHCO-, R ^1d and R ^2d may together form a ring containing a nitrogen atom, R ^3d and R ^4d may form a ring containing a nitrogen atom together, but adjacent -CH ₂ - not While being replaced with similar groups, addition, -CH ends ₂ - will not be replaced, R ^5d represents ^{_{-OH, -SO 3 -, -SO 3}} H, -SO 3 - Zd +, -CO 2 H, -CO ₂ ^- Zd ⁺ , -CO ₂ R ^8d , -SO ₃ R ^8d or -SO ₂ NR ^9d R ^10d , R ^6d and R ^7d independently of each other represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and md represents An integer of 0 to 5, and when md is 2 or more, a plurality of R ^5d may be the same or different, d represents an integer of 0 or 1, Xd represents a halogen atom, and Zd ⁺ represents ⁺ N(R ^11d ) ₄ , Na ⁺ or K ⁺ , 4 R ^11d may be the same or different, and R ^8d represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and R ^9d and R ^10d are independently of each other. A hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO-, -NR ^11d -, -OCO- , -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-, R ^9d and R ^10d may be bonded to each other to form a 3 to 10 membered ring heterocyclic ring containing a nitrogen atom, however, adjacent - CH ₂ - is replaced at the same time not similar groups, addition, -CH ends ₂ - will not be In other words, R ^11d represents a hydrogen atom, a C monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10. A colored curable resin composition, comprising: the dye solution according to any one of claims 1 to 7, a resin (B), a polymerizable compound (C), and a polymerization initiator (D) . A color filter formed of the colored curable resin composition of claim 8. A display device comprising the color filter of claim 9.