KR102114958B1 - Method for preparing dye solution, colored curable resin composition comprising the dye solution, color filters, and display devices - Google Patents

Abstract

The present invention provides a method for preparing a solution of xanthene dye having excellent stability over time, a color curable resin composition including the xanthene dye solution, a color filter, and a display device. The method for preparing a dye solution of the present invention comprises a step of agitating at least one member selected from the group consisting of (a) xanthene dye and (b) organic acid salt and silicon atom-containing compound in the presence of an organic solvent. Is done.

Description

Method for preparing a dye solution, colored curable resin composition including the dye solution, color filter, and display device{Method for preparing dye solution, colored curable resin composition comprising the dye solution, color filters, and display devices}

The present invention relates to a method for preparing a dye solution, a colored curable resin composition containing the dye solution, a color filter, and a display device.

In the fields of textile materials, liquid crystal displays, inkjets, and the like, dyes are used to display colors using reflected light or transmitted light. Rhodamine B represented by the following formula (Rb) having a xanthene skeleton is widely known as such a dye (non-patent document 1).

[Formula 1]

[Advanced technical literature]

``New Dye Chemistry'' by Yutaka Hosoda, Gidodo (1), 1st edition, May 1973, 274

When using a xanthene dye for the above-mentioned use, from the viewpoint of uniform coloration, the xanthene dye is generally used in a solution state dissolved in an organic solvent. However, it was found that the xanthene dye itself was difficult to dissolve in an organic solvent, and when the solution containing the xanthene dye was stored as it was, a precipitate formed due to changes over time even for about a week. It was a problem that the dye solution containing the precipitate could not be used for the above application.

In this situation, it is an object of the present invention to provide a method for preparing a solution of xanthene dye having excellent stability over time.

This invention has the following summary.

[1] Preparation of a dye solution comprising a step of stirring at least one selected from the group consisting of (a) xanthene dye and (b) organic acid salt and silicon atom-containing compound in the presence of an organic solvent. Way.

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

[3] The compound of [1] or [2], wherein the organic acid is an aliphatic carboxylic acid, an aromatic carboxylic acid, an aliphatic sulfonic acid, an alicyclic sulfonic acid, an aromatic sulfonic acid, a compound represented by the following formula (h1), and the following formula (h2). At least one member selected from the compound represented by, and the aliphatic carboxylic acid, the aromatic carboxylic acid, the aliphatic sulfonic acid and hydrogen atoms other than the acidic protons constituting the aromatic sulfonic acid may be substituted with a halogen atom or a hydroxyl group, -CH ₂ -constituting the aliphatic carboxylic acid, aliphatic sulfonic acid and the alicyclic sulfonic acid is a method for producing a dye solution that can be substituted with -CO-.

[Formula 2]

[In formula (h1), X ^h1 and X ^h2 independently represent a fluorine atom or a C 1-4 fluorinated alkyl group, or X ^h1 and X ^h2 are combined to form a C 2-4 fluorinated alkanediyl group. .

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

[4] The method according to any one of [1] to [3], wherein the silicon atom-containing compound is a compound represented by the following formula (j).

[Formula 3]

[In formula (j),

R ^h1 represents a hydrogen atom, a hydroxy 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 ^h1s may be the same or different, respectively,

R ^h2 represents a monovalent substituent.]

[5] The method for producing a dye solution according to any one of [1] to [4], wherein the organic solvent is a carboxylic acid ester of an alkylene glycol monoalkyl ether, an aliphatic alcohol having a ketone carbonyl group, or a mixed solvent thereof.

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

[Formula 4]

[In formula (1a),

R ¹ to R ⁴ are, independently of each other, a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or formula (ii) Indicates the displayed group.

*-R ⁵⁰ -Si(R ²⁹ ) ₃ (ii)

(In formula (ii), R ²⁹ represents a hydrogen atom, a hydroxy 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 may be the same or different.

R ⁵⁰ represents an alkanediyl group having 1 to 10 carbon atoms, and -CH ₂ -constituting the alkanediyl group is -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH- , -NHCOO-, -CONH- or -NHCO-. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.

* Indicates a valent bond with a nitrogen atom.)

-CH ₂ -contained in the saturated hydrocarbon group of R ¹ to R ⁴ is -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-, R ¹ and R ² together may form a ring containing a nitrogen atom, R ³ and R ⁴ together may form a ring containing a nitrogen atom. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.

R ⁵ is _{^{-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 the integer of 0-5. When m is 2 or more, a plurality of R ⁵ may be the same or different.

a represents the integer of 0 or 1.

X represents a halogen atom.

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

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

R ⁹ and R ¹⁰ each independently 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 is -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH, -NHCOO-, -CONH- or -NHCO- can be substituted, R ⁹ and R ¹⁰ are bonded to each other, 3 to 10 membered ring containing nitrogen atom hetero Can form a ring. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.

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 according to any one of [1] to [6], wherein the xanthene dye is a compound represented by the following formula (1d).

[Formula 5]

[In formula (1d),

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

*-R ⁵⁰ -Si(R ²⁹ ) ₃ (ii)

(In 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 may be the same or different.

R ⁵⁰ represents an alkanediyl group having 1 to 10 carbon atoms, and -CH ₂ -constituting the alkanediyl group is -O-, -CO-, -NR ^11d -, -OCO-, -COO-, -OCONH- , -NHCOO-, -CONH- or -NHCO-. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.

* Indicates a bond with a nitrogen atom.)

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

R ^5d is _{^{-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 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

md represents the integer of 0-5. When md is 2 or more, a plurality of R ^5ds may be the same or different.

d represents the integer of 0 or 1.

Xd represents a halogen atom.

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

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

R ^9d and R ^10d represent, independently of each other, a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and -CH ₂ -contained in the saturated hydrocarbon group is -O-, -CO-,- NR ^11d -, -OCO-, -COO-, -OCONH, -NHCOO-, -CONH- or -NHCO- can be substituted, and R ^9d and R ^10d are bonded to each other to form a 3 to 10-membered ring containing a nitrogen atom. Hetero rings can be formed. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.

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] A colored curable resin composition comprising a dye solution prepared by any one of [1] to [7], a resin (B), a polymerizable compound (C), and a polymerization initiator (D). .

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

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

According to the method for preparing a dye solution according to the present invention, it is possible to suppress the occurrence of foreign matter due to the change over time of the dye solution obtained, so it is stable against the change over time. Therefore, the dye solution to be prepared can be applied to various fields such as dyes for colored curable compositions.

The method for preparing the dye solution of the present invention

(a) Xanthene dye

(b) characterized in that it comprises a step of stirring at least one member selected from the group consisting of salts of organic acids and silicon atom-containing compounds in the presence of an organic solvent.

By stirring the xanthene dye (a) with at least one selected from the group consisting of organic acid salts and silicon atom-containing compounds (b), the xanthene dye (a) alone can exhibit stability stability over time that cannot be achieved.

<Production method of dye solution>

The dye solution obtained in the present invention comprises at least one organic solvent selected from the group consisting of (a) xanthene dyes and (b) organic acid salts and silicon atom-containing compounds. And this dye solution can be obtained by stirring at least one member selected from the group consisting of (a) xanthene dye, (b) organic acid salt and silicon atom-containing compound.

<Xanthene dye (a)>

The xanthene dye (a) used in the present invention is a dye containing a compound having a xanthene skeleton in a molecule, and the xanthene dye (a) is a compound represented by formula (1a) (hereinafter referred to as compound (1a)) Dyes containing) are preferred. The compound (1a) may be a tautomer.

[Formula 4]

[In formula (1a),

R ¹ to R ⁴ are, independently of each other, a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or formula (ii) Indicates the displayed group.

*-R ⁵⁰ -Si(R ²⁹ ) ₃ (ii)

(R ²⁹ represents a hydrogen atom, a hydroxy 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 may be the same or different.

R ⁵⁰ represents an alkanediyl group having 1 to 10 carbon atoms, and -CH ₂ -constituting the alkanediyl group is -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH- , -NHCOO-, -CONH- or -NHCO-. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.

* Indicates a bond with a nitrogen atom.)

-CH ₂ -contained in the saturated hydrocarbon group of R ¹ to R ⁴ is -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-, R ¹ and R ² together may form a ring containing a nitrogen atom, R ³ and R ⁴ together may form a ring containing a nitrogen atom. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.

R ⁵ is _{^{-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 the integer of 0-5. When m is 2 or more, a plurality of R ⁵ may be the same or different.

a represents the integer of 0 or 1.

X represents a halogen atom.

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

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

R ⁹ and R ¹⁰ each independently 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 is -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH, -NHCOO-, -CONH- or -NHCO- can be substituted, R ⁹ and R ¹⁰ are bonded to each other, 3 to 10 membered ring containing nitrogen atom hetero Can form a ring. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.

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.]

When -SO ₃ ^- is present in formula (1a), the number is one.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms of 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. As the substituent which may have aromatic hydrocarbon groups wherein the halogen ^{atoms, -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 , and it is preferable that such substituents are substituted with hydrogen atoms contained in aromatic hydrocarbon groups. Among them, as the substituent is _{^{-R 8, -SO 3 -, -SO}} 3 H, -SO 3 - Z + and -SO ₂ NR ⁹ R ¹⁰ are _{^{preferred, -R 8, -SO 3 - Z}} + and -SO ₂ NR ⁹ R ¹⁰ is more preferable. As -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. Also, -SO ₃ ^-+ N(R ¹¹ ) ₄ is preferred as -SO ₃ ^- Z ⁺ in this case.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms of R ¹ to R ⁴ and R ⁸ to R ¹¹ is a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group or decyl group , A straight-chain alkyl group such as dodecyl group, hexadecyl group and icosyl group; Branched chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group; And alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and tricyclodecyl group.

-CH ₂ -contained in the saturated hydrocarbon group may be substituted with -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH, -NHCOO-, -CONH- or -NHCO- have. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.

The following are mentioned as a group in which -CH ₂ -contained in the saturated hydrocarbon group is substituted with -O- (* represents a bond).

[Formula 6]

The following are mentioned as a group in which -CH ₂ -contained in the saturated hydrocarbon group is substituted with -CO- (* represents a bond).

[Formula 7]

The following are mentioned as a group in which -CH ₂ -contained in the saturated hydrocarbon group is substituted with -NR ¹¹ -(* represents a bond).

[Formula 8]

The following are mentioned as a group in which -CH ₂ -contained in the saturated hydrocarbon group is substituted with -OCO- (* represents a bond).

[Formula 9]

The following are mentioned as a group in which -CH ₂ -contained in the saturated hydrocarbon group is substituted with -COO- (* represents a bond).

[Formula 10]

The following may be mentioned as a group in which -CH ₂ -contained in the saturated hydrocarbon group is substituted with -OCONH- (* represents a bond).

[Formula 11]

The following are mentioned as a group in which -CH ₂ -contained in the saturated hydrocarbon group is substituted with -NHCOO- (* represents a bond).

[Formula 12]

The following are mentioned as a group in which -CH ₂ -contained in the saturated hydrocarbon group is substituted with -CONH- (* represents a bond).

[Formula 13]

The following may be mentioned as a group in which -CH ₂ -contained in the saturated hydrocarbon group is substituted with -NHCO- (* represents a bond).

[Formula 14]

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

The hydrogen atom contained in the saturated hydrocarbon group of R ⁹ and R ¹⁰ may be substituted with a hydroxy group or a halogen atom as a substituent.

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

[Formula 15]

Examples of -OR ⁸ include alkyloxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, and isoxyloxy group. have.

Examples of -CO ₂ R ⁸ include alkyloxycarbonyl such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, tert-butoxycarbonyl group, hexyloxycarbonyl group, and isoxyloxycarbonyl group.

Examples of -SR ⁸ include alkylsulfanyl groups such as methylsulfanyl group, ethylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, decylsulfanyl group, and isosilsulfanyl group.

Examples of -SO ₂ R ⁸ include alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, decylsulfonyl group, and isocosylsulfonyl group.

Examples of -SO ₃ R ⁸ include alkoxysulfonyl groups such as methoxysulfonyl group, ethoxysulfonyl group, propoxysulfonyl group, tert-butoxysulfonyl group, hexyl oxysulfonyl group, and oxysiloxyl sulphonyl group. Can be.

-SO ₂ NR ⁹ R ¹⁰ is, for example, a sulfamoyl group;

N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulfa Moyl group, N-tert-butyl sulfamoyl group, N-pentyl sulfamoyl group, N-(1-ethylpropyl) sulfamoyl group, N-(1,1-dimethylpropyl) sulfamoyl group, N-(1, 2-dimethylpropyl)sulfamoyl group, N-(2,2-dimethylpropyl)sulfamoyl group, N-(1-methylbutyl)sulfamoyl group, N-(2-methylbutyl)sulfamoyl group, N-( 3-methylbutyl)sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N-(1,3-dimethylbutyl)sulfamoyl group, N-(3,3-dimethylbutyl)sulfamo Diary, N-heptylsulfamoyl group, N-(1-methylhexyl)sulfamoyl group, N-(1,4-dimethylpentyl)sulfamoyl group, N-octylsulfamoyl group, N-(2-ethylhexyl) N-1 substituted sulfamoyl groups such as sulfamoyl group, N-(1,5-dimethylhexyl) sulfamoyl group and N-(1,1,2,2-tetramethylbutyl) sulfamoyl group;

N,N-dimethylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-propylmethylsulfamoyl group, N,N-isopropylmethylsulfamoyl group, N, such as N,N-tert-butylmethylsulfamoyl group, N,N-butylethylsulfamoyl group, N,N-bis(1-methylpropyl)sulfamoyl group and N,N-heptylmethylsulfamoyl group, And N-2 substituted sulfamoyl groups.

Roneun R ^{5 _{-CO 2 H, -CO 2 - Z}} +, -CO 2 R 8, -SO 3 -, -SO 3 - Z +, -SO 3 H and -SO ₂ NHR ⁹ are preferred, -SO ₃ ^-, -SO ₃ ^- is Z ^+, -SO ₃ H and -SO ₂ NHR ⁹ is more preferable.

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

In the compound (1a), a compound in which the phenyl group substituted with the (R ⁵ )m group in the formula (1a) is one of formulas (R ⁵ -1) to (R ⁵ -37) is preferred, and the formula (R ⁵ -1) ) ~ A compound of formula (R ⁵ -25) is more preferred, a compound of formula (R ⁵ -1) to formula (R ⁵ -5) is more preferred, a formula (R ⁵ -1) of Compounds are particularly preferred. Further, R ⁴⁰ and R ⁴¹ in the formulas (R ⁵ -1) to (R ⁵ -37) independently of each other represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably branched with 6 to 12 carbon atoms. It is a chain alkyl group, More preferably, it is a 2-ethylhexyl group.

[Formula 16]

[Formula 17]

Examples of the alkyl group having 1 to 6 carbon atoms of R ⁶ and R ⁷ include groups having 1 to 6 carbon atoms among the alkyl groups mentioned above.

Hydrogen atoms are preferred as R ⁶ and R ⁷ .

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

[Formula 18]

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 for the ⁺ N(R ¹¹ ) _4, it is preferable that at least two of four R ¹¹ are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. In addition, the total number of carbon atoms of the four R ¹¹ is preferably 20-80, more preferably 20-60. When ⁺ N(R ¹¹ ) ₄ is present in compound (1a), when R ¹¹ is such a group, the color curable resin composition of the present invention including compound (1a) can form a color filter with few foreign substances.

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 it is 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 hydroxy 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 may be the same or different.

R ⁵⁰ represents an alkanediyl group having 1 to 10 carbon atoms, and -CH ₂ -constituting the alkanediyl group is -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH- , -NHCOO-, -CONH- or -NHCO-. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.

* Indicates a bond with a nitrogen atom.)

R ²⁹ represents a hydrogen atom, a hydroxy 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 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 tert-butoxy group.

R ²⁹ is preferably a hydroxy group and an alkoxy group having 1 to 4 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group, a methoxy group and an ethoxy group, and particularly preferably a methoxy group and an ethoxy group.

The alkanediyl group having 1 to 10 carbon atoms represented by R ⁵⁰ is a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an isopropylene group, an isobutylene group, and 2-methyltrimethylene group. Group, isopentylene group, isohexylene group, isooctylene group, 2-ethylhexylene group, and the like, preferably an alkanediyl group having 1 to 6 carbon atoms, more preferably 1 to 1 carbon number. And an alkanediyl group of 4.

-CH ₂ -constituting the alkanediyl group represented by R ⁵⁰ is -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-. However, the adjacent -CH ₂ -is not simultaneously substituted with the same group, and the terminal -CH ₂ -may not be substituted.

Examples of the group represented by formula (ii) include groups represented by the following formulas (ii-1) to (ii-24).

[Formula 19]

[Formula 20]

In the formula (ii), a group represented by the following may be mentioned as a group in which -CH ₂ -constituting R ⁵⁰ is substituted with -O- (* represents a bond).

[Formula 21]

[Formula 22]

In the formula (ii), the group represented by the following is a group in which -CH ₂ -constituting R ⁵⁰ is substituted with -CO- (* represents a bonding hand).

[Formula 23]

[Formula 24]

In the formula (ii), a group represented by the following is a group in which -CH ₂ -constituting R ⁵⁰ is substituted with -NR ¹¹ -(* represents a bond).

[Formula 25]

[Formula 26]

In the formula (ii), a group represented by the following may be mentioned as a group in which -CH ₂ -constituting R ⁵⁰ is substituted with -OCO- (* represents a bond).

[Formula 27]

[Formula 28]

In the formula (ii), a group represented by the following is a group in which -CH ₂ -constituting R ⁵⁰ is substituted with -COO- (* represents a bonding hand).

[Formula 29]

[Formula 30]

In the formula (ii), the group represented by the following is a group in which -CH ₂ -constituting R ⁵⁰ is substituted with -OCONH- (* represents a bonding hand).

[Formula 31]

[Formula 32]

In the formula (ii), a group represented by the following is a group in which -CH ₂ -constituting R ⁵⁰ is substituted with -NHCOO- (* represents a bond).

[Formula 33]

[Formula 34]

In the formula (ii), a group represented by the following is a group in which -CH ₂ -constituting R ⁵⁰ is substituted with -CONH- (* represents a bond).

[Formula 35]

[Formula 36]

In the formula (ii), a group represented by the following is a group in which -CH ₂ -constituting R ⁵⁰ is substituted with -NHCO- (* represents a bond).

[Formula 37]

[Formula 38]

When the compound (1a) that have a substituent represented by the formula (ii), formula (ii) the R ²⁹ is a hydroxy group or preferably an alkoxy group having from 1 to 4 carbon atoms and, R ²⁹ is a hydroxy group or an alkoxy group having from 1 to 4 carbon atoms And R ⁵⁰ is a substituent having an alkanediyl group having 1 to 10 carbon atoms, and more preferably a substituent represented by the following formula (i).

[Formula 39]

(In formula (i),

n represents an integer from 1 to 8,

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 a bond with a nitrogen atom.)

n is preferably 1 to 6, more preferably 1 to 5, and even more preferably 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.

As R ^{12, a} hydrogen atom, a methyl group, an ethyl group, and a propyl group are preferable, and a hydrogen atom, a methyl group, and an ethyl group are more preferable.

Examples of the group represented by formula (i) include groups represented by the following formulas (i-1) to (i-12). The group represented by formula (i) includes a group represented by formula (i-2), a group represented by formula (i-3), a group represented by formula (i-5), and represented by formula (i-6) The group to be used is preferred, and more preferably a group represented by formula (i-3).

[Formula 40]

The compound represented by the formula (1a) is represented by the following formula (1a-1) having no substituent represented by the formula (ii) depending on the presence or absence of the group represented by the formula (ii) in R ¹ to R ⁴ It can be classified as a compound represented by the following formula (1a-2) having a compound and a substituent represented by formula (ii). Hereinafter, the more preferable compound of each of the compound represented by the following formula (1a-1) and the compound represented by the following formula (1a-2) will be described.

[Formula 4]

Equation (1a-1):

R ¹ to R ⁴ in the formula (1a) are independently of each other, a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. -CH ₂ -contained in the saturated hydrocarbon group of R ¹ to R ⁴ is -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH -Or -NHCO-, R ¹ and R ² together may form a ring containing a nitrogen atom, R ³ and R ⁴ together may form a ring containing a nitrogen atom,

R ⁵ to R ¹¹ , m, a, X, and Z ⁺ are the same compounds as described above.

Equation (1a-2):

R ¹ to R ⁴ in the formula (1a) are independently of each other, a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms that may have a substituent. Or a group represented by formula (ii), and at least one of R ¹ to R ⁴ is a group represented by formula (ii). -CH ₂ -contained in the saturated hydrocarbon group of R ¹ to R ⁴ is -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-, R ¹ and R ² together may form a ring containing a nitrogen atom, R ³ and R ⁴ together may form a ring containing a nitrogen atom.

R ⁵ to R ¹¹ , R ²⁹ , R ⁵⁰ , m, a, X, and Z ⁺ are the same compounds as described above.

As the compound represented by formula (1a-1), for example, a compound represented by the following formula (1b) (hereinafter referred to as "compound (1b)") is preferable. The compound (1b) may be a tautomer.

[Formula 41]

[In formula (1b),

R ^1b ~ R ^4b represent, independently of each other, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent,

-CH ₂ -contained in the saturated hydrocarbon group of R ^1b to R ^4b is -O-, -CO-, -NR ^11b -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-, and R ^1b and R ^2b together may form a ring containing a nitrogen atom, and R ^3b and R ^4b together may form a ring containing a nitrogen atom. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.

R ^5b is _{^{-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 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

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

b represents the 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 the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

R ^9b and R ^10b each independently 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 is -O-, -CO-,- NR ^11b -, -OCO-, -COO-, -OCONH, -NHCOO-, -CONH- or -NHCO- can be substituted, and R ^9b and R ^10b are bonded to each other to form a 3-10 membered ring containing a nitrogen atom. Hetero rings can be formed. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.

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.]

When -SO ₃ ^- is present in formula (1b), the number is one.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms of R ^1b to R ^4b and R ^8b to R ^11b is a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group or decyl group. , A straight-chain alkyl group such as dodecyl group, hexadecyl group and icosyl group; Branched chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group; And alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and tricyclodecyl group.

-CH ₂ -contained in the saturated hydrocarbon group may be substituted with -O-, -CO-, -NR ^11b -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO- Can be. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.

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

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

Compound (1b) in the R ^1b ~ R ^4b of R ^1b and R ^2b, R ^3b and R ^4b is preferably a saturated hydrocarbon group such as, respectively, and, for example, R ^1b and R ^2b, R ^3b and R ^4b are each straight- The combination which is a chain alkyl group is preferable, More preferably, R ^1b and R ^2b , R ^3b and R ^4b are each a combination having a linear alkyl group having 1 to 5 carbon atoms, and more preferably R ^1b and R ^2b , R ^3b and R ^4b is a combination of two selected from the group consisting of a methyl group, an ethyl group, a propyl group, and a butyl group, respectively.

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

[Formula 42]

Examples of -OR ^8b include alkyloxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and isoxyloxy group. have.

As -CO ₂ R ^8b (substituents not mentioned in the detailed description, please confirm.) Alkoxy oxy such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, tert-butoxycarbonyl group, hexyloxycarbonyl group and icosyloxycarbonyl group Carbonyl and the like.

Examples of -SR ^8b include alkylsulfanyl groups such as methylsulfanyl group, ethylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, decylsulfanyl group and eicosylsulfanyl group.

Examples of -SO ₂ R ^8b include alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, decylsulfonyl group and eicosylsulfonyl group.

Examples of -SO ₃ R ^8b include alkoxysulfonyl groups such as methoxysulfonyl group, ethoxysulfonyl group, propoxy sulphonyl group, tert-butoxysulfonyl group, hexyl oxysulfonyl group and eicosil oxysulfonyl group. Can be.

-SO ₂ NR ^9b R ^10b is, for example, a sulfamoyl group;

N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulfa Moyl group, N-tert-butyl sulfamoyl group, N-pentyl sulfamoyl group, N-(1-ethylpropyl) sulfamoyl group, N-(1,1-dimethylpropyl) sulfamoyl group, N-(1, 2-dimethylpropyl)sulfamoyl group, N-(2,2-dimethylpropyl)sulfamoyl group, N-(1-methylbutyl)sulfamoyl group, N-(2-methylbutyl)sulfamoyl group, N-( 3-methylbutyl)sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N-(1,3-dimethylbutyl)sulfamoyl group, N-(3,3-dimethylbutyl)sulfamo Diary, N-heptylsulfamoyl group, N-(1-methylhexyl)sulfamoyl group, N-(1,4-dimethylpentyl)sulfamoyl group, N-octylsulfamoyl group, N-(2-ethylhexyl) N-1 substituted sulfamoyl groups such as sulfamoyl group, N-(1,5-dimethylhexyl) sulfamoyl group, N-(1,1,2,2-tetramethylbutyl) sulfamoyl group;

N,N-dimethylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-propylmethylsulfamoyl group, N,N-isopropylmethylsulfamoyl group, N, such as N,N-tert-butylmethylsulfamoyl group, N,N-butylethylsulfamoyl group, N,N-bis(1-methylpropyl)sulfamoyl group, N,N-heptylmethylsulfamoyl group, And N-2 substituted sulfamoyl groups.

R ^5b roneun ^{_{-CO 2 H, -CO 2 - Zb}} +, -CO 2 R 8b, -SO 3 -, -SO 3 - Zb +, -SO 3 H or -SO ₂ NHR ^9b are preferred, -SO ₃ ^-, -SO ₃ ^- it is Zb ^+, -SO ₃ H or -SO ₂ NHR ^9b is more preferable.

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

It is preferable that the phenyl group substituted with the (R ^5b )mb group also in compound (1b) is one of the aforementioned (R ⁵ -1) to formula (R ⁵ -37), and the formulas (R ⁵ -1) to formula (R ⁵⁾ It is more preferable that it is one of -25), it is more preferable that it is one of formulas (R ⁵ -1) to formula (R ⁵ -5), and a compound of formula (R ⁵ -1) is particularly preferred.

Examples of the alkyl group having 1 to 6 carbon atoms in R ^6b and R ^7b include groups having 1 to 6 carbon atoms among the above-mentioned alkyl groups. Especially, a hydrogen atom is preferable as R ^6b and R ^7b .

R ^9b and R ^10b may represent a nitrogen-containing 3 to 10-membered ring heterocycle together with the nitrogen atom. As said hetero ring, the following is mentioned, for example.

[Formula 43]

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 for the ⁺ N(R ^11b ) _4, it is preferable that at least two of the four R ^11b are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. Moreover, it is preferable that the total carbon number of four ^R11b is 20-80, and it is more preferable that it is 20-60.

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

b is 0 or 1, preferably 0.

Moreover, as a compound represented by Formula (1a-1), for example, a compound represented by the following Formula (1c) (hereinafter referred to as "compound (1c)") is preferable. The compound (1c) may be a tautomer.

[Formula 44]

[In formula (1c),

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

R ^2c and R ^3c represent, independently of each other, a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent,

-CH ₂ -contained in the saturated hydrocarbon group of R ^2c and R ^3c is -O-, -CO-, -NR ^11c -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.

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

R ^5c is -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 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

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

c represents the 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 the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

R ^9c and R ^10c represent, independently of each other, a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and -CH ₂ -contained in the saturated hydrocarbon group is -O-, -CO-,- NR ^11c -, -OCO-, -COO-, -OCONH, -NHCOO-, -CONH- or -NHCO-, and R ^9c and R ^10c are bonded to each other to form a 3 to 10-membered ring containing a nitrogen atom. Hetero rings can be formed. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.

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.]

When -SO ₃ ^- is present in formula (1c), the number is one.

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

Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ^1c and R ^4c include methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, butylsulfanyl group, and isopropylsulfanyl group.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ^1c and R ^4c include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group and isopropylsulfonyl group.

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 integers of 0 to 2, more preferably 1 or 2.

As the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms of R ^2c , R ^3c and R ^8c to R ^11c , a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group , A straight-chain alkyl group such as dodecyl group, hexadecyl group and icosyl group; Branched chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; And alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and tricyclodecyl group.

-CH ₂ -contained in the saturated hydrocarbon group may be substituted with -O-, -CO-, -NR ^11c -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO- Can be. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.

The hydrogen atom contained in the saturated hydrocarbon group of R ^2c and R ^3c may be substituted with 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 capable of substituting the hydrogen atom of the saturated hydrocarbon group of R ^2c and R ^3c include groups such as those exemplified by the aromatic hydrocarbon group having 6 to 10 carbon atoms of R ¹ to R ⁴ .

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

Examples of -OR ^8c include alkyloxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and icosyloxy group. have.

Examples of -CO ₂ R ^8c include alkyloxycarbonyl such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, tert-butoxycarbonyl group, hexyloxycarbonyl group, and isoxyloxycarbonyl group.

Examples of -SR ^8c include alkylsulfanyl groups such as methylsulfanyl group, ethylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, decylsulfanyl group, and icosylsulfanyl group.

Examples of -SO ₂ R ^8c include alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, decylsulfonyl group, and ecosylsulfonyl group.

Examples of -SO ₃ R ^8c include alkoxysulfonyl groups such as methoxysulfonyl group, ethoxysulfonyl group, propoxysulfonyl group, tert-butoxysulfonyl group, hexyl oxysulfonyl group, and oxysiloxyl sulphonyl group. Can be.

-SO ₂ NR ^9c R ^10c is, for example, a sulfamoyl group;

N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulfa Moyl group, N-tert-butyl sulfamoyl group, N-pentyl sulfamoyl group, N-(1-ethylpropyl) sulfamoyl group, N-(1,1-dimethylpropyl) sulfamoyl group, N-(1, 2-dimethylpropyl)sulfamoyl group, N-(2,2-dimethylpropyl)sulfamoyl group, N-(1-methylbutyl)sulfamoyl group, N-(2-methylbutyl)sulfamoyl group, N-( 3-methylbutyl)sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N-(1,3-dimethylbutyl)sulfamoyl group, N-(3,3-dimethylbutyl)sulfamo Diary, N-heptylsulfamoyl group, N-(1-methylhexyl)sulfamoyl group, N-(1,4-dimethylpentyl)sulfamoyl group, N-octylsulfamoyl group, N-(2-ethylhexyl) N-1 substituted sulfamoyl groups such as sulfamoyl group, N-(1,5-dimethylhexyl) sulfamoyl group, N-(1,1,2,2-tetramethylbutyl) sulfamoyl group;

N,N-dimethylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-propylmethylsulfamoyl group, N,N-isopropylmethylsulfamoyl group, N, such as N,N-tert-butylmethylsulfamoyl group, N,N-butylethylsulfamoyl group, N,N-bis(1-methylpropyl)sulfamoyl group, N,N-heptylmethylsulfamoyl group, And N-2 substituted sulfamoyl groups.

R ^5c roneun ^{_{-CO 2 H, -CO 2 - Zc}} +, -CO 2 R 8c, -SO 3 -, -SO 3 - Zc +, -SO 3 H or -SO ₂ NHR ^9c is preferably, -SO ₃ ^-, -SO ₃ ^- it is Zc ^+, -SO ₃ H or -SO ₂ NHR ^9c is more preferable.

mc is preferably 1 to 4, and more preferably 1 or 2.

In the compound (1c), it is preferable that the phenyl group substituted with the (R ^5c )mc group is one of the aforementioned (R ⁵ -1) to formula (R ⁵ -37), and the formulas (R ⁵ -1) to formula (R ⁵⁾ It is more preferable that it is one of -25), it is more preferable that it is one of formulas (R ⁵ -1) to (R ⁵ -5), and it is particularly preferable that it is formula (R ⁵ -1).

Examples of the alkyl group having 1 to 6 carbon atoms in R ^6c and R ^7c include those having 1 to 6 carbon atoms among the above-mentioned alkyl groups. Especially, a hydrogen atom is preferable as R ^6c and R ^7c .

R ^9c and R ^10c may represent a nitrogen-containing 3 to 10-membered ring heterocycle together with the nitrogen atom. As said hetero ring, the following is mentioned, for example.

[Formula 45]

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 .

It is preferable that at least 2 of 4 R ^11c are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms as the ⁺ N(R ^11c ) ₄ . Moreover, it is preferable that the total carbon number of four ^R11c is 20-80, and it is more preferable that it is 20-60.

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, preferably 0.

Moreover, as a compound represented by Formula (1a-2), for example, a compound represented by the following Formula (1d) (hereinafter referred to as "compound (1d)") is preferable. The compound (1d) may be a tautomer.

[Formula 5]

[In formula (1d),

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

*-R ⁵⁰ -Si(R ²⁹ ) ₃ (ii)

(R ²⁹ represents a hydrogen atom, a hydroxy 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 may be the same or different.

R ⁵⁰ represents an alkanediyl group having 1 to 10 carbon atoms, and -CH ₂ -constituting the alkanediyl group is -O-, -CO-, -NR ^11d -, -OCO-, -COO-, -OCONH- , -NHCOO-, -CONH- or -NHCO-. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.

* Indicates a bond with a nitrogen atom.)

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

R ^5d is _{^{-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 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

md represents the integer of 0-5. When md is 2 or more, a plurality of R ^5ds may be the same or different.

d represents the integer of 0 or 1.

Xd represents a halogen atom.

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

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

R ^9d and R ^10d represent, independently of each other, a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and -CH ₂ -contained in the saturated hydrocarbon group is -O-, -CO-,- NR ^11d -, -OCO-, -COO-, -OCONH, -NHCOO-, -CONH- or -NHCO- can be substituted, and R ^9d and R ^10d are bonded to each other to form a 3 to 10-membered ring containing a nitrogen atom. Hetero rings can be formed. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.

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.]

When -SO ₃ ^- is present in equation (1d), the number is one.

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

As the substituent group which may have the aromatic hydrocarbon is 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 , and it is preferable that such a substituent is a hydrogen atom contained in an aromatic hydrocarbon group. Among the by substituent is _{^{-SO 3 -, -SO 3 H,}} -SO 3 - is Zd ⁺ and -SO ₂ NR ^9d R ^10d, and preferably, SO ₃ ^- Zd ⁺ and -SO ₂ NR ^9d R ^10d is more preferable . As SO ₃ ^- Zd ^{+ in} this case, -SO ^3-+ N(R ^11d )4 is preferable.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms of R ^1d to R ^4d and R ^8d to R ^11d is a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group or decyl group. , Straight-chain alkyl groups such as dodecyl group, hexadecyl group, and icosyl group; Branched chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group; And alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and tricyclodecyl group.

-CH ₂ -contained in the saturated hydrocarbon group may be substituted with -O-, -CO-, -NR ^11d -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO- You can. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.

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

The hydrogen atom contained in the saturated hydrocarbon group of R ^9d and R ^10d may be substituted with a hydroxy group or a halogen atom as a substituent.

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

[Formula 46]

R ^1d ~ R ^4d at least one is a group represented by the formula (ii), other R ^1d ~ R ^4d roneun is methyl, ethyl, propyl, 1-methylphenyl, 1,5-dimethylphenyl group, and more preferably It is a methyl group, an ethyl group, and a propyl group.

Examples of -OR ^8d include alkyloxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, and isoxyloxy group. have.

Examples of -CO ₂ R ^8d include alkyl oxycarbonyl such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, tert-butoxycarbonyl group, hexyloxycarbonyl group, and isoxyloxycarbonyl group.

Examples of -SR ^8d include alkylsulfanyl groups such as methylsulfanyl group, ethylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, decylsulfanyl group and icosylsulfanyl group.

Examples of -SO ₂ R ^8d include alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, decylsulfonyl group, and icosylsulfonyl group.

Examples of -SO ₃ R ^8d include alkoxysulfonyl groups such as methoxysulfonyl group, ethoxysulfonyl group, propoxysulfonyl group, tert-butoxysulfonyl group, hexyl oxysulfonyl group, and icosyloxysulfonyl group. You can.

-SO ₂ NR ^9d R ^10d is, for example, a sulfamoyl group;

N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulfa Moyl group, N-tert-butyl sulfamoyl group, N-pentyl sulfamoyl group, N-(1-ethylpropyl) sulfamoyl group, N-(1,1-dimethylpropyl) sulfamoyl group, N-(1, 2-dimethylpropyl)sulfamoyl group, N-(2,2-dimethylpropyl)sulfamoyl group, N-(1-methylbutyl)sulfamoyl group, N-(2-methylbutyl)sulfamoyl group, N-( 3-methylbutyl)sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N-(1,3-dimethylbutyl)sulfamoyl group, N-(3,3-dimethylbutyl)sulfamo Diary, N-heptylsulfamoyl group, N-(1-methylhexyl)sulfamoyl group, N-(1,4-dimethylpentyl)sulfamoyl group, N-octylsulfamoyl group, N-(2-ethylhexyl) N-1 substituted sulfamoyl groups such as sulfamoyl group, N-(1,5-dimethylhexyl) sulfamoyl group, N-(1,1,2,2-tetramethylbutyl) sulfamoyl group;

N,N-dimethylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-propylmethylsulfamoyl group, N,N-isopropylmethylsulfamoyl group, N, such as N,N-tert-butylmethylsulfamoyl group, N,N-butylethylsulfamoyl group, N,N-bis(1-methylpropyl)sulfamoyl group, N,N-heptylmethylsulfamoyl group, And N-2 substituted sulfamoyl groups.

R ^5d roneun ^{_{-CO 2 H, -CO 2 - Zd}} +, -CO 2 R 8d, -SO 3 -, -SO 3 - Zd +, -SO 3 H or -SO ₂ NHR ^9d are preferred, -SO ₃ ^-, -SO ₃ ^- is Zd ^+, -SO ₃ H or -SO ₂ NHR ^9d is more preferable.

md is preferably 1 to 4, and more preferably 1 or 2.

It is preferable that the compound (1d) is also one of the aforementioned (R ⁵ -1) to formula (R ⁵ -37), the phenyl group substituted with the (R ^5d )md group of formula (1d), and the formula (R ⁵ -1) It is more preferably one of formulas (R ⁵ -25), more preferably one of formulas (R ⁵ -1) to (R ⁵ -5), and particularly preferably formula (R ⁵ -1) Do.

Examples of the alkyl group having 1 to 6 carbon atoms of R ^6d and R ^7d include those having 1 to 6 carbon atoms among the above-mentioned alkyl groups. Especially, a hydrogen atom is preferable as R ^6d and R ^7d .

R ^9d and R ^10d may represent a nitrogen-containing 3 to 10-membered ring heterocycle together with the nitrogen atom. As said hetero ring, the following is mentioned, for example.

[Formula 47]

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 for the ⁺ N(R ^11d ) _4, it is preferable that at least two of the four R ^11d are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. Moreover, it is preferable that the total carbon number of four ^R11d is 20-80, and it is more preferable that it is 20-60.

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, preferably 0.

In addition, the substituents represented by formula (ii) of R ^1d to R ^4d are the same as described above in formula (1a).

Among the above-mentioned xanthene dyes (1d), more preferable examples include compounds represented by the following formula (2d);

[Formula 5]

[In formula (2d),

R ^1d to R ^4d represent, independently of each other, 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 group represented by formula (ii), and R ^1d to R At least one of ^4d is a group represented by formula (ii).

*-R ⁵⁰ -Si(R ²⁹ ) ₃ (ii)

(R ²⁹ represents a hydrogen atom, a hydroxy 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 may be the same or different.

R ⁵⁰ represents an alkanediyl group having 1 to 10 carbon atoms, and -CH ₂ -constituting the alkanediyl group is -O-, -CO-, -NR ^11d -, -OCO-, -COO-, -OCONH- , -NHCOO-, -CONH- or -NHCO-. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.

* Indicates a bond with a nitrogen atom.)

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

R ^5d is _{^{-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 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

md represents the integer of 0-5. When md is 2 or more, a plurality of R5ds may be the same or different.

d represents the integer of 0 or 1.

Xd represents a halogen atom.

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

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

R ^9d and R ^10d represent, independently of each other, a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and -CH ₂ -contained in the saturated hydrocarbon group is -O-, -CO-,- NR ^11d -, -OCO-, -COO-, -OCONH, -NHCOO-, -CONH- or -NHCO- can be substituted, and R ^9d and R ^10d are bonded to each other to form a 3 to 10-membered ring containing a nitrogen atom. Hetero rings can be formed. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.

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.]

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

[Formula 49]

[In formula (3d),

R ^1d to R ^4d represent, independently of each other, 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 group represented by formula (i), and R ^1d to R At least one of ^4d is a group represented by formula (i).

[Formula 50]

(In formula (i),

n represents an integer from 1 to 8,

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 a valent bond with a nitrogen atom.)

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

R ^5d is _{^{-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 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

md represents the integer of 0-5. When md is 2 or more, a plurality of R ^5ds may be the same or different.

d represents the integer of 0 or 1.

Xd represents a halogen atom.

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

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

R ^9d and R ^10d represent, independently of each other, a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and -CH ₂ -contained in the saturated hydrocarbon group is -O-, -CO-,- NR ^11d -, -OCO-, -COO-, -OCONH, -NHCOO-, -CONH- or -NHCO- can be substituted, and R ^9d and R ^10d are bonded to each other to form a 3 to 10-membered ring containing a nitrogen atom. Hetero rings can be formed. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.

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.]

Preferred compounds as the xanthene dye (1a) as described above include, for example, compounds represented by the following formulas (I-1) to (I-170). In the formula, R ⁴⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group.

Among them, as a xanthene dye (1a), more preferably, R ¹ to R ⁴ have one substituent represented by formula (ii), and the remaining group is a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. (For example, compounds (I-1) to (I-4), (I-13) to (I-16), (I-25) to (I-28), (I-37) to (I -40), (I-55) to (I-110), (I-117), (I-120), etc.), and two substituents represented by formula (ii) in R ¹ to R ⁴ exist and the rest Compounds in which the group is a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (for example, compounds (I-49) to (I-54), compounds (I-111) to (I-116), compounds ( I-119), (I-121), (I-122), etc.), compounds having two xylyl groups at R ¹ to R ⁴ (e.g., compounds (I-124) to (I-146), (I-151), (I-153), (I-155), (I-156), etc.), compounds having two tolyl groups in R ¹ to R ⁴ (e.g., compound (I-147), (I-150), (I-152), (I-154), etc.), wherein R ¹ to R ⁴ are all monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms which may have substituents (for example, compounds ( I-160) to (I-170).

Preferably 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) to (I-167).

[Formula 51]

[Formula 52]

[Formula 53]

[Formula 54]

[Formula 55]

[Formula 56]

[Formula 57]

[Formula 58]

[Formula 59]

[Formula 60]

[Formula 61]

[Formula 62]

[Formula 63]

[Formula 64]

[Formula 65]

[Formula 66]

[Formula 67]

[Formula 68]

[Formula 69]

[Formula 70]

[Formula 71]

[Formula 72]

Xanthene dye (a) is a commercially available xanthene dye (e.g., ``Chugai Aminol Fast Pink RH/C'' manufactured by Chugai Chemical Co., Ltd., ``Rhodamin 6G'' manufactured by Takaoka Chemical Industries, Ltd.). Can be used. In addition, commercially available xanthene dyes can be synthesized as a starting material by reference to Japanese Unexamined Patent Publication No. 2010-32999.

Such xanthene dye (a) is, for example, C.I. Acid Red 51 (hereinafter referred to as C.I. Acid Red is omitted and described only by number. Others are the same.), C.I. of 52, 87, 92, 94, 289, 388, etc. Acid dyes; C.I. C.I. of Acid Violet 9, 30, 102, etc. Acid violet dyes; C.I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, 10 (Rhodamine B), 11, etc. C.I. Basic red dye; C.I. Basic Violet 10, 11, 25, etc. C.I. Basic violet dyes; C.I. Solvent Red 218 et al. C.I. Solvent red dye; C.I. C.I. Modern red dye; C.I. Reactive Red 36 (Rose Bengal B) et al. C.I. Reactive red dye; Sulforhodamine G; Xanthene dyes described in Japanese Patent Application Laid-open No. 2010-32999; And xanthene dyes described in Patent No. 4242760; And the like.

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

<Salt of organic salt>

The salt of the organic acid used in the present invention is selected from aliphatic carboxylic acids, aromatic carboxylic acids, aliphatic sulfonic acids, alicyclic sulfonic acids, aromatic sulfonic acids, compounds represented by the following formula (h1) and compounds represented by the following formula (h2) It is a salt of at least one organic acid, and the hydrogen atoms other than the acidic protons 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 hydroxy group, etc. Carboxylic acid, aliphatic sulfonic acid and -CH ₂ -constituting the alicyclic sulfonic acid may be substituted with -CO-.

[Formula 2]

[In formula (h1), X ^h1 and X ^h2 independently represent a fluorine atom or a C 1-4 fluorinated alkyl group, or X ^h1 and X ^h2 are combined to form a C 2-4 fluorinated alkanediyl group. .

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

Aliphatic carboxylic acid is a compound R ²¹ (COOH)x (where x is an integer of 1 or more, more preferably 1, 2 or 3, and more preferably 1 or 2) having a carboxy group (-COOH), wherein R ²¹ is It means an aliphatic hydrocarbon group or formic acid. Examples of the aliphatic carboxylic acid include saturated fatty acids having 1 to 25 carbon atoms, unsaturated carboxylic acids having 1 to 25 carbon atoms, and the like. Saturated fatty acids having 1 to 25 carbon atoms include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, capronic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid and lauric acid; Aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid; And the like. Further, examples of the unsaturated carboxylic acid having 1 to 25 carbon atoms include oleic acid, linoleic acid, linolenic acid, arachidonic acid, docosahexaenoic acid, eicosapentanoic acid, fumaric acid, and maleic acid.

The aromatic carboxylic acid is R ^{22 among} compounds R ²² (COOH)x (x is an integer of 1 or more, more preferably 1, 2 or 3, and more preferably 1 or 2) having a carboxy group (-COOH), wherein R ²² is It is an aliphatic hydrocarbon group. Examples of R ²² include an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and preferably a phenyl group having a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. Examples of such aromatic carboxylic acids include benzoic acid, toluic acid, dimethylbenzoic acid, diethylbenzoic acid, dipropylbenzoic acid, dibutylbenzoic acid, phthalic acid, isophthalic acid, telephthalic acid, naphthalenedicarboxylic acid, and the like.

Examples of the alicyclic sulfonic acid include cyclohexane sulfonic acid, 4-methylcyclohexane sulfonic acid, and bicyclo[2.2.1]-hepta-2-ene-5-sulfonic acid.

Aliphatic sulfonic acid is compound R ²³ (SO ₃ H))x having sulfo group (-SO ₃ H) x (x is an integer of 1 or more, preferably 1, 2 or 3, more preferably 1 or 2) In the above, it is said that R ²³ is an aliphatic hydrocarbon group. Examples of the aliphatic sulfonic acid include aliphatic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, octanesulfonic acid, nonanesulfonic acid and decansulfonic acid. Monosulfonic acid; Aliphatic disulfonic acids such as methane disulfonic acid, ethane disulfonic acid, propane disulfonic acid, butane disulfonic acid, propane disulfonic acid, and hexane disulfonic acid; And the like.

Aromatic sulfonic acid is a compound R ²⁴ (SO ₃ H))x having a sulfo group (-SO ₃ H) x (x is an integer of 1 or more, preferably 1, 2 or 3, more preferably 1 or 2) In the above, it means that R ²⁴ is an aromatic hydrocarbon group. Examples of the aromatic sulfonic acid include benzenesulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid.

Hydrogen atoms other than the acidic protons 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 halogen atoms capable of substituting hydrogen atoms other than the acidic protons of the aliphatic carboxylic acid, the aromatic carboxylic acid, the aliphatic sulfonic acid, and the aromatic sulfonic acid include F, Cl, Br, I, and fluorine is particularly preferable. These acids 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 substituted with -CO-, and these acids include 10-camphorsulfonic acid.

In addition, X ^h1 and X ^h2 in the formula (h1) are each independently a fluorine atom or a C 1-4 fluorinated alkyl group. Further, X ^h3 to X ^h5 in the formula (h2) independently of each other represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms.

Examples of the fluorinated alkyl group having 1 to 4 carbon atoms include, for example, the substituents shown below, among them, *-CF ₂ CF ₃ , *-CF ₂ CF ₂ CF ₃ and *-CF ₂ CF ₂ CF ₂ CF ₃ is preferred, and *-CF ₂ CF ₂ CF ₃ and *-CF ₂ CF ₂ CF ₂ CF ₃ are more preferred.

[Formula 73]

Moreover, X ^h1 and X ^h2 may combine X ^h1 and X ^h2 to form a C 2-4 fluorinated alkanediyl group. As the fluorinated alkanediyl group having 2 to 4 carbon atoms, a substituent represented by *-(CF ₂ )n-* is preferable (where n is an integer of 2-4).

Salts of the various organic acids described above include alkali metal salts such as lithium salts, sodium salts, potassium salts, and cesium salts; Alkaline earth metal salts such as calcium salts; Metal salts such as zinc salt and copper salt; Quaternary ammonium salts; And so on.

Salts of these organic acids include salts of benzoic acid, which may have substituents represented by the following formulas (h0-1) to (h0-21), compounds represented by the following formulas (h1-1) to (h1-8), and the following formula ( The compounds represented by h2-1) to (h2-8) are preferred.

[Formula 74]

[Formula 75]

[Formula 76]

Among the salts of organic acids, salts of the compounds represented by the formula (h0-13), compounds represented by the formula (h1), or compounds represented by the formula (h2) are particularly preferred, and more preferably the formula zinc salt of (h0-13), bis(trifluoromethanesulfonyl)imide lithium or tris(trifluoromethanesulfonyl)methide lithium.

<Silicon atom-containing compound>

The compound represented by the following formula (j) is mentioned as a silicon atom containing compound. In the present invention, the "silicon atom-containing compound" shall also include the "condensate" of the compound represented by the following formula (j).

[Formula 3]

[In formula (j),

R ^h1 represents a hydrogen atom, a hydroxy 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 ^h1s may be the same or different, respectively,

R ^h2 represents a monovalent 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, which may be straight 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. A methoxy group and an ethoxy group are preferable, and an ethoxy group is more preferable from the viewpoint of contributing to stability over time.

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

R ^h2 is a monovalent substituent. As R ^h2 , saturated hydrocarbon groups having 1 to 10 carbon atoms, aromatic hydrocarbon groups having 6 to 10 carbon atoms, or vinyl groups, epoxy groups, methacryl groups, acrylic groups, amino groups, isocyanurate groups, ureido groups, mercapto groups, and sulfides It is preferably a substituent containing at least one functional group selected from the group consisting of groups and isocyanate groups. The functional group contained in R ^h2 is preferably bonded to the Si atom in the silicon atom-containing compound (j) through 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. .

The saturated hydrocarbon group of 1 to 10 carbon atoms of R ^h2 is preferably a saturated hydrocarbon group of 2 to 9 carbon atoms, more preferably a saturated hydrocarbon group of 4 to 8 carbon atoms, more preferably a pentyl group, hexyl group, hep It is a tyl group or octyl group. The hydrogen atom constituting the saturated hydrocarbon group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, or a substituent such as *-Si(R ^h3 ) ₃ (where R ^h3 is an alkoxy group having 1 to 4 carbon atoms). Can be.

The aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^h2 is 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, more preferably 1 to 10 carbon atoms. It is a saturated hydrocarbon group of 3.

A phenylene group is preferable as the divalent aromatic hydrocarbon group having 6 to 10 carbon atoms contained in R ^h2 .

As such R ^h2 , for example, the substituents shown below are preferable, and among them, R ^h2 is preferably 3-methacryloxypropyl group, N-methyl-3-aminopropyl group, N-phenyl-3-aminopropyl group and octyl. Group is preferred.

[Formula 77]

[Formula 78]

Silane atom-containing compounds include silane coupling agents and silane compounds.

Examples of the silane coupling agent include vinyl silane coupling agents such as vinyl trimethoxysilane and vinyl triethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, Epoxy-based silane coupling agents such as 3-glycidoxypropyl triethoxysilane; styryl-based silane coupling agents such as p-styryl trimethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltri (Meth)acrylic silane coupling agents such as methoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltri Ethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-methyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrime Amino silane coupling agents such as oxysilane; Ureido-based silane coupling agents such as 3-ureidopropyl trialkoxysilane; Mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; Sulfide type silane coupling agents such as bis(triethoxysilylpropyl)tetrasulfide; Isocyanate-based silane coupling agents such as 3-isocyanatepropyltriethoxysilane; And the like.

In addition, as the silane compound, for example, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, propyltrimethoxysilane, propyltree Ethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, 1,6-bis(trimethoxysilyl ) Alkoxysilanes such as hexane.

Among them, a (meth)acrylic silane coupling agent, an amino silane coupling agent, and an alkoxysilane are preferred as the silicon atom-containing compound, more preferably 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyl tree Methoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-methyl-3- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, Octyltriethoxysilane, decyltrimethoxysilane, and more preferably 3-methacryloxypropyltrimethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltri Methoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, particularly preferably 3-methacryloxypropyltrimethoxysilane, N-methyl-3- Aminopropyl trimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, and octyl trimethoxysilane.

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

In addition, in the case where both the salt of the organic acid and the silicon atom-containing compound are used in combination as the component (b), the amount of the salt of the organic acid is preferably 1 to 50 parts by mass, more preferably 5 to 5 parts by mass, based on 100 parts by mass of the total xanthene dye. 40 mass parts, More preferably, it is 10-30 mass parts. The amount of the silicon atom-containing compound is preferably 200 to 1000 parts by mass, more preferably 300 to 800 parts by mass, and even more preferably 400 to 700 parts by mass, based on 100 parts by mass of the amount of organic acid salt used (total).

<Organic solvent>

The organic solvent used in the present invention is not particularly limited as long as it is a solvent obtained by dissolving the aforementioned xanthene dye (a), and an ester solvent (a solvent containing -COO- in the molecule and no containing -O-), Ether solvent (solvent containing -O- in the molecule and not containing -COO-), ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (containing -CO- in the molecule) And solvents not containing -COO-), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc. Can be heard.

Ester solvents include methyl lactic acid, ethyl lactic acid, butyl lactic acid, 2-hydroxyisobutanoic acid methyl ester, ethyl acetate, butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionic acid, isopropyl butyric acid, ethyl butyric acid, butyl And butyric acid, methylpyruvic acid, ethylpyruvic acid, propylpyruvic acid, methyl acetoacetic acid, ethyl acetoacetic acid, cyclohexanol acetate and γ-butyrolactone.

Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and 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 methylethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenitol and methylanisole And the like.

Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl-3-methoxypropionic acid, ethyl-3-methoxypropionic acid, methyl-3- Ethoxypropionic acid, ethyl-3-ethoxypropionic acid, methyl-2-methoxypropionic acid, ethyl-2-methoxypropionic acid, propyl-2-methoxypropionic acid, methyl-2-ethoxypropionic acid, ethyl-2-ethoxy Propionic acid, methyl-2-methoxy-2-methylpropionic acid, ethyl-2-ethoxy-2-methylpropionic acid, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate , Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether Acetate is mentioned.

As a ketone solvent, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2 -Pentanone, cyclopentanone, cyclohexanone, isophorone, etc. are mentioned.

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

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

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

These solvents may be used alone or in combination of a plurality of solvents. Especially, use of an ether ester solvent, a ketone solvent, an alcohol solvent, and these mixed solvents is preferable, and the use of an ether ester solvent, a ketone solvent, and these mixed solvents is more preferable.

As the ether ester solvent, carboxylic acid esters of alkylene glycol monoalkyl ethers such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate Is preferred, and propylene glycol monomethyl ether acetate is more preferred.

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

<Preparation of dye solution>

In the present invention, as the component (b), at least one kind of a salt of an organic acid and a compound containing a silicon atom may be used, and only one kind selected from a salt of an organic acid and a compound containing a silicon atom may be used, and a salt and a silicon atom of an organic acid are contained. You may use together 2 or more types chosen from a compound. Examples of the use form of the component (b) include a form using a salt of an organic acid, a form using only a silicon atom-containing compound, and a form using a combination of both a salt of an organic acid and a silicon atom-containing compound.

In the form using a salt of an organic acid or a form using only a silicon atom-containing compound, the method for preparing a composition (mixture) comprising the (a) xanthene dye and these (b) components is not particularly limited, and the preparation of the composition As a method, for example, (b) adding a xanthene dye to a mixed solution containing a component and an organic solvent; (a) adding a component (b) to a mixed solution containing a xanthene dye and an organic solvent; And the like.

In the form in which both the salt of the organic acid and the silicon atom-containing compound are used in combination, the method for adding the xanthene (a) and the silicon atom-containing compound is not particularly limited, for example, a silicon atom-containing compound in the presence of a salt of the organic acid. After adding and stirring (it is called stirring process 1), the method of adding a xanthene dye (a); A method of adding and stirring the xanthene dye (a) in the presence of a salt of an organic acid (hereinafter referred to as a stirring step 2), and then adding a silicon atom-containing compound; A method of adding a xanthene dye (a) and a silicon atom-containing compound in the presence of a salt of an organic acid; And the like.

In the stirring step 1 to 2, the stirring time is 30 minutes or more, preferably 1 hour or more, more preferably 2 hours or more, and the upper limit is not particularly limited, but is usually 20 hours or less.

In addition, in order to increase the solubility of the silicon atom-containing compound in an organic solvent, the mixture may be heated to 30 to 60 either before or after the addition of the silicon atom-containing compound.

The composition comprising at least one selected from the group consisting of the salts of the (a) xanthene dye and (b) organic acid and a silicon atom-containing compound thus obtained is stirred in the presence of an organic solvent.

The stirring time is not particularly limited, but, for example, 1 hour or more is preferable, more preferably 3 hours or more, still more preferably 5 hours or more, particularly preferably 10 hours or more, and 100 hours or less It is preferred, more preferably 90 hours or less, still more preferably 80 hours or less, even more preferably 60 hours or less, particularly preferably 40 hours or less, and most preferably 30 hours or less.

In addition, when the xanthene dye (a) is treated only with a salt of an organic acid, the stirring time is preferably 2 hours or more, more preferably 3 hours or more, preferably 80 hours or less, more preferably 60 hours or less And more preferably 40 hours or less, particularly preferably 30 hours or less.

In addition, when the xanthene dye (a) is treated with only a silicon atom-containing compound or a combination of a salt of an organic acid and a silicon atom-containing compound, the stirring time is preferably 5 hours or more, more preferably 10 hours or more, 30 The time is preferably less, and more preferably 20 hours or less.

The stirring temperature is not particularly limited, but -10 or more is preferable, 0 or more is more preferable, 10 or more is more preferable, 20 or more is particularly preferable, 80 or less is preferable, 70 or less is more preferable, 60 or less is more preferable.

<Solid-liquid separation process>

In the present invention, a solid-liquid separation process for removing insoluble matter may be performed after the stirring process. Examples of solid-liquid separation include filtration, centrifugation, and combinations thereof, and it is particularly preferable to perform filtration in the present invention in that it is easy to operate. Examples of the filtration method include natural filtration, pressure filtration, and vacuum filtration.

Filtration may use a filter aid. The filter aid may be any method such as pre-coat or body feed. Filtration aids include activated clay, silica, diatomaceous earth, celite, pearlite, cellulose, activated carbon, alumina, magnesium silicate, aluminum hydroxide, hydrotalcite, aluminum silicate, magnesium and aluminum-based solid solutions, and ceramics. And awsonite.

<Color curable resin composition>

The dye dissolving solution (A1) is useful as a dye, and is particularly useful as a colorant of the color curable resin composition used in color filters of display devices such as liquid crystal displays.

The content of the xanthene dye (a) in the dye solution (A1) contained in the color curable resin composition forming the color filter is preferably 0.025 mass% or more and 48 mass% or less with respect to the total solid content of the color curable resin composition, 0.08 mass% or more and 42 mass% or less are more preferable, and 0.1 mass% or more and 30 mass% or less are more preferable.

In the present specification, the "total amount of solid content" refers to the total amount of components excluding the solvent (E) from the colored curable resin composition of the present invention. The total amount of solid content and the content of each component thereof can be measured by a known analytical method 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 (D).

It is preferable that the coloring agent (A) contains the pigment (P) in addition to the dye solution (A1). Here, a dye (A2) different from the xanthene dye (a) included in the dye solution (A1) may be further included.

The content of the xanthene dye (a) in the colorant (A) is preferably 0.01% by mass or more and 90% by mass or less, more preferably 0.1% by mass or more and 80% by mass or less with respect to the total amount of the colorant (A).

<Pigment (P)>

The pigment (P) is not particularly limited, and known pigments can be used, and compounds classified as pigments in the color index (published by The Society of Dyers and Colourists) are mentioned.

As a pigment, C.I. Pigment Yellow 1 (hereinafter, the description of CI Pigment Yellow will be omitted, and only the number will be described.), 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, Yellow pigments such as 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;

C.I. Pigments of orange such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 175, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. Red pigment;

C.I. Pigment Blue 15, 15; 3. Blue pigments such as 15:4, 15:6, 60, and 80;

C.I. Violet pigments such as pigment violet 1, 19, 23, 29, 32, 36, 38;

C.I. Green pigments such as Pigment Green 7, 36, and 58;

C.I. Pigments such as Pigment Brown 23 and 25;

C.I. And black pigments such as Pigment Black 1 and 7.

These pigments can be used alone or in combination of two or more.

As a pigment, C.I. Yellow pigments such as Pigment Yellow 138, 139, and 150; C.I. Red pigments such as Pigment Red 177, 242, and 254; C.I. Pigment Blue 15, 15; 3. Blue pigments such as 15:4, 15:6, and 60; And C.I. Violet pigments such as pigment violet 1, 19, 23, 29, 32, 36, 38; Is preferred, more preferably C.I. Pigment Blue 15, 15; 3. 15:4, 15:6 and at least one selected from the group consisting of pigment violet 23, more preferably C.I. At least one member selected from the group consisting of Pigment Blue 15:6 and Pigment Violet 23. The inclusion of the pigment makes it easy to optimize the transmission spectrum of the color filter using the colored curable resin composition of the present invention, and the heat resistance, light resistance and chemical resistance of the color filter are improved.

It is preferable that the coloring curable resin composition of this invention contains a blue pigment.

Pigments are treated with rosin, surface treatment using pigment derivatives with acidic or basic groups introduced as necessary, graft treatment to pigment surfaces with polymeric compounds, atomization treatment with sulfuric acid atomization, or organic solvents to remove impurities B may be a washing treatment with water or the like, or a removal treatment with an ion exchange method for ionic impurities. It is preferable that the pigment particle diameters are uniform.

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

The pigment dispersion liquid can be obtained by mixing a pigment and a pigment dispersant in a solvent.

In the above-mentioned mixing, two or more kinds of pigments may be mixed, or may be mixed alone, or a plurality of kinds may be mixed.

The pigment dispersant may be any of cationic, anionic, nonionic and amphoteric dispersants, and pigment dispersants such as polyester, polyamine, and acrylic.

These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersant, KP (made by Shin-Etsu Chemical Industry Co., Ltd.), Proren (manufactured by Gongyoung Chemical Co., Ltd.), Solsperth (manufactured by Geneca Co., Ltd.), EFKA (manufactured by BASF), Azisper (Ajinomoto Fine) Techno Co., Ltd.), Disperbyk (manufactured by BIC Chemie), and the like.

It does not specifically limit as said solvent, The solvent like the solvent of the colored curable resin composition of this invention is mentioned.

When a pigment dispersant is used, the amount used 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. When the amount of the pigment dispersant used is in the above range, a pigment dispersion liquid in which the pigment is uniformly dispersed in a solvent can be obtained.

<Dye (A2)>

The dye (A2) includes dyes such as fat-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes, published by The Society of Dyers and Colourists ), or a known dye described in a dyeing note (color irradiation). Here, according to the chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squwarium dye, acridine dye , Styryl dye, coumarin dye, quinoline dye and nitro dye. Of these, organic solvent-soluble dyes are preferred.

Specifically, C.I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;

C.I. Solvent red 45, 49, 125, 130, 218;

C.I. Solvent orange 2, 7, 11, 15, 26, 56;

C.I. Solvent blue 4, 5, 37, 67, 70, 90;

C.I. C.I. of Solvent Green 1, 4, 5, 7, 34, 35, etc. Solvent dyes;

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

C.I. Acid 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;

C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

C.I. Acid violet 6B, 7, 9, 17, 19, 30, 102;

C.I. 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; C.I. Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. C.I. Acid dyes;

C.I. 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;

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

C.I. Direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

C.I. Direct Blue 1, 2, 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;

C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. C.I. Direct dyes;

C.I. C.I. of Impulse Yellow 54, 76, etc. Disperse dyes;

C.I. Basic red 1, 10;

C.I. Basic Blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;

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

C.I. Reactive Yellow 2, 76, 116;

C.I. Reactive Orange 16;

C.I. Reactive Red 36; C.I. Reactive dyes;

C.I. Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C.I. Modern 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;

C.I. Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

C.I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

C.I. Modern 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;

C.I. C.I. of Modern Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, etc. Modern dyes;

C.I. Bart Green 1 et al. C.I. And bart dyes.

Among them, blue dye, violet dye and red dye are preferred.

These dyes may be appropriately selected according to the spectral spectrum of the desired color filter. These dyes may be used alone or in combination of two or more.

The content rate of the colorant (A) is preferably 1% by mass or more, more preferably 5% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50 with respect to the total amount of solid content. It is less than mass%. When the content of the colorant (A) is within the above range, desired spectroscopy and color concentration can be obtained.

<Resin (B)>

Although it does not specifically limit as resin (B), It is preferable that it is alkali-soluble resin (B). The alkali-soluble resin (B) (hereinafter 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 unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides.

The following resin [K1]-[K6] etc. are mentioned as such resin (B).

Resin [K1]: a structural unit derived from at least one monomer (a) (hereinafter referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and a cyclic ether structure having 2 to 4 carbon atoms, A copolymer having a structural unit derived from a monomer (b) having an ethylenically unsaturated bond (hereinafter referred to as "(b)");

Resin [K2]: A structural unit derived from (a), a structural unit derived from (b), and a monomer (c) copolymerizable with (a) (however, different from (a) and (b)). (b3)”);

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 derived from (c) and a structural unit obtained by adding (b) to a structural unit derived from (a);

Resin [K5]: a copolymer having a structural unit derived from (c) and a structural unit obtained by adding (a) to a structural unit derived from (b);

Resin [K6]: A copolymer having a structural unit derived from (c) and a structural unit additionally added with carboxylic acid anhydride by adding (a) to the structural unit derived from (b);

(a) includes unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hepto-2-ene, 5,6-dicarboxybicyclo[2.2.1]hepto-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hepto-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hepto-2-ene, 5-carboxy-6-methylbicyclo[ 2.2.1] bicyclo unsaturated compounds containing carboxyl groups such as hepto-2-ene and 5-carboxy-6-ethylbicyclo[2.2.1]hepto-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , Unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hepto-2-ene anhydride;

Unsaturated mono[(meth)acryloyloxyalkyl of divalent or higher polyvalent carboxylic acids such as mono[2-(meth)acryloyloxyethyl]succinic acid, mono[2-(meth)acryloyloxyethyl]phthalic acid ]Esters;

and unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylate.

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

(b) includes a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Can be.

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

Here, "(meth)acrylic acid" in this specification represents at least 1 sort(s) selected from the group which consists of acrylic acid and methacrylic acid. Notations such as "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

As (b), a monomer having an oxiranyl group and an ethylenically unsaturated bond (b1) (hereinafter referred to as "(b1)"), a monomer having an oxetanyl group and an ethylenically unsaturated bond (b2) (hereinafter referred to as "(b2)" And a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (b3) (hereinafter referred to as "(b3)").

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

As (b1-1), glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinyl benzyl glycol Cydyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, α-methyl-o-vinylbenzylglycidyl ether, α-methyl-m-vinylbenzylglycidyl ether, α- Methyl-p-vinylbenzylglycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl) )Styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2 ,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene and 2,4,6-tris(glycidyloxymethyl)styrene. have.

As (b1-2), vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meta )Acrylate (for example, cyclomer A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, cyclomer M100; manufactured by Daicel Co., Ltd.), The compound represented by Formula (II), the compound represented by Formula (III), etc. are mentioned.

[Formula 79]

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

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

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

* Represents a bonding hand with O.]

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

As the alkyl group in which the hydrogen atom is substituted with hydroxy, a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy And hydroxy-1-methylethyl groups, 2-hydroxy-1-methylethyl groups, 1-hydroxybutyl groups, 2-hydroxybutyl groups, 3-hydroxybutyl groups, and 4-hydroxybutyl groups.

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

Examples of the alkanediyl group having 1 to 6 carbon atoms include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, and pentane-1,5-di group. Diary, hexane-1,6-diyl group, etc. are mentioned.

X ^a and X ^b preferably include a single bond, a methylene group, an ethylene group, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, more preferably a single bond, *-CH _{And 2} CH ₂ -O- (* indicates a bond with O).

Examples of the compound represented by formula (II) include compounds represented by any one of formulas (II-1) to (II-15). Among them, preferably, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II) The compound represented by -15) is mentioned, More preferably, the compound represented by Formula (II-1), Formula (II-7), Formula (II-9), and Formula (II-15) is mentioned. have.

[Formula 80]

[Formula 81]

Examples of the compound represented by formula (III) include compounds represented by any one of formulas (III-1) to (III-15). Among them, preferably, formula (III-1), formula (III-3), formula (III-5), formula (III-7), formula (III-9) or formula (III-11) to formula (III) The compound represented by -15) is mentioned, More preferably, the compound represented by Formula (III-1), Formula (III-7), Formula (III-9), and Formula (III-15) is mentioned. have.

[Formula 82]

[Formula 83]

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

As (b2), a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferable. (b2) 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3- Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacrylo Iloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, etc. are mentioned.

As (b3), a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable. As (b3), specifically, tetrahydrofurfuryl acrylate (for example, biscoat V #150, manufactured by Osaka Organic Chemical Industries, Ltd.), tetrahydrofurfuryl methacrylate, and the like can be mentioned.

As (b), it is preferable that it is (b1) in that the reliability, such as heat resistance and chemical resistance, of the obtained color filter can be further improved. In addition, (b1-2) is more preferable from the viewpoint of excellent storage stability of the colored curable resin composition.

As (c), methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl ( Meta)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (Meth)acrylate, tricyclo[5.2.1.O ^2,6 ]decane-8-yl(meth)acrylate (known in the art as dicyclopentanyl (meth)acrylate as a common name. Cyclodecyl (meth)acrylate”), tricyclo[5.2.1.O ^2,6 ]decene-8-yl(meth)acrylate (In the art, the common name is "dicyclopentenyl (( Meta)acrylate), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, aryl (meth)acrylate, propargyl (Meth)acrylic acid esters such as (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate and benzyl (meth)acrylate;

(Meth)acrylic acid esters containing hydroxy groups such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

Diester dicarboxylic acids such as diethyl maleic acid, diethyl fumaric acid, and diethyl itaconic acid;

Bicyclo[2.2.1]hepto-2-ene, 5-methylbicyclo[2.2.1]hepto-2-ene, 5-ethylbicyclo[2.2.1]hepto-2-ene, 5-hydroxy ratio Cyclo[2.2.1]hepto-2-ene, 5-hydroxymethylbicyclo[2.2.1]hepto-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hepto-2 -Ene, 5-methoxybicyclo[2.2.1]hepto-2-ene, 5-ethoxybicyclo[2.2.1]hepto-2-ene, 5,6-dihydroxybicyclo[2.2.1]hepto -2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hepto-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hepto- 2-ene, 5,6-dimethoxybicyclo[2.2.1]hepto-2-ene, 5,6-diethoxybicyclo[2.2.1]hepto-2-ene, 5-hydroxy-5-methyl Bicyclo[2.2.1]hepto-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1] Hepto-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hepto-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hepto-2-ene, 5-phenoxy Cycarbonylbicyclo[2.2.1]hepto-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hepto-2-ene and 5,6-bis(cyclohexyloxy Bicyclo unsaturated compounds such as cycarbonyl)bicyclo[2.2.1]hepto-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutylate, N-succinimidyl Dicarbonylimide derivatives such as -6-maleimide capriate, N-succinimidyl-3-maleimide propionate, and N-(9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl Acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Among them, styrene, vinyl toluene, benzyl (meth)acrylate, tricyclo[5.2.1.O ^2,6 ]decane-8-yl(meth)acrylate, N-phenylmaleimide, in terms of copolymerization reactivity and heat resistance, N-cyclohexylmaleimide, N-benzylmaleimide and bicyclo[2.2.1]hepto-2-ene are preferred.

In resin [K1], the proportion of structural units derived from each is among the total structural units constituting resin [K1].

structural unit derived from (a); 2 to 60 mol%

structural units derived from (b); 40 ~ 98 mol%

Is preferably,

structural unit derived from (a); 10 to 50 mol%

structural units derived from (b); 50 ~ 90 mol%

It is more preferable.

In the resin [K1], when the proportion of the structural unit is in the above range, the storage stability of the colored curable resin composition, developability at the time of forming a colored pattern, and solvent resistance of the resulting color filter tend to be excellent.

Resin [K1] is a method described in the literature "Experiment for Polymer Synthesis" (Otsu Takayuki, published by Chemical Dongin Co., Ltd., 1st edition, 1st printing, published March 1, 1972) and the citations described in the literature It can be prepared with reference to.

The specific method for producing the resin [K1] is a method in which a predetermined amount of (a) and (b), a polymerization initiator, a solvent, etc. are placed in a reaction vessel to replace oxygen with nitrogen to form a deoxygenated atmosphere, and heated and kept warm while stirring. Can be heard.

In addition, the polymerization initiator, solvent, and the like used herein are not particularly limited, and may be used commonly used in the field. Polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile, etc.)) and organic peroxides (benzoyl peroxide, etc.), As a solvent, what is necessary is just to be able to melt|dissolve each monomer, and the solvent (E) of the colored curable resin composition of this invention contains the solvent mentioned later.

Moreover, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, or may use what was extracted as a solid (powder) by methods, such as reprecipitation. In particular, during the polymerization, by using the solvent contained in the colored curable resin composition of the present invention as a solvent, the solution after the reaction can be used as it is for the production of the colored curable resin composition of the present invention, thereby producing the colored curable resin composition of the present invention. The process can be simplified.

In resin [K2], the proportion of structural units derived from each is among the total structural units constituting resin [K2].

structural unit derived from (a); 2 to 45 mol%

structural units derived from (b); 2 to 95 mol%

structural unit derived from (c); 1 to 65 mol%

Is preferably,

structural unit derived from (a); 5 to 40 mol%

structural units derived from (b); 5 to 80 mol%

structural unit derived from (c); 5 to 60 mol%

It is more preferable.

When the proportion of the structural unit of the resin [K2] is within the above range, the storage stability of the color curable resin composition, developability at the time of forming a colored pattern, and solvent resistance, heat resistance and mechanical strength of the resulting color filter tend to be excellent.

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

In resin [K3], the proportion of structural units derived from each is among the total structural units constituting resin [K3].

structural unit derived from (a); 2 to 60 mol%

structural unit derived from (c); 40 ~ 98 mol%

Is preferably,

structural unit derived from (a); 10 to 50 mol%

structural unit derived from (c); 50 ~ 90 mol%

It is more preferable.

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

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

First, the copolymers of (a) and (c) are prepared in the same manner as described for the method for producing resin [K1]. At this time, the ratio of the structural unit derived from each is preferably the same ratio as the ratio mentioned in the resin [K3].

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

Following the preparation of the copolymers of (a) and (c), the atmosphere in the flask is replaced by nitrogen to air, and (b), a reaction catalyst of carboxylic acid or carboxylic acid anhydride with a cyclic ether (e.g. tris(dimethylaminomethyl)phenol Etc.) and a polymerization inhibitor (for example, hydroquinone, etc.) into a flask, and reacted at 60 to 130 for 1 to 10 hours to produce resin [K4].

The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol (a). By setting it as this range, the balance of the storage stability of a colored curable resin composition, the developability at the time of pattern formation, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern becomes favorable. (B1) is preferable as (b) used for resin [K4], and (b1-1) is more preferable because the reactivity of the cyclic ether is high and unreacted (b) is difficult to remain.

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

The reaction conditions such as the preparation method, reaction temperature and time can be appropriately adjusted in consideration of the production facility and the amount of heat generated by polymerization. In addition, in the same manner as the polymerization conditions, the preparation method and the reaction temperature can be appropriately adjusted in consideration of the production facilities and the amount of heat generated by polymerization.

Resin [K5] is the first step, and a copolymer of (b) and (c) is obtained in the same manner as in the above-mentioned production method of resin [K1]. As described above, the obtained copolymer may use the solution after the reaction as it is, or may use a concentrated or diluted solution, or may be used as a solid (powder) extracted by a method such as reprecipitation.

The proportions of the structural units derived from (b) and (c) are each relative to the total number of moles of the total structural units constituting the copolymer.

structural units derived from (b); 5 to 95 mol%

structural unit derived from (c); 5 to 95 mol%

Is preferably,

structural units derived from (b); 10 ~ 90 mol%

structural unit derived from (c); 10 ~ 90 mol%

It is more preferable.

Furthermore, by reacting the carboxylic acid or carboxylic acid anhydride of (a) with the cyclic ether derived from (b) of the copolymer of (b) and (c) under the same conditions as the method for producing resin [K4], the resin [ K5].

The amount of (a) used to react with the copolymer is preferably 5 to 80 moles per 100 moles (b). (B1) is preferred as (b) used for the resin [K5], and (b1-1) is more preferable because the reactivity of the cyclic ether is high and unreacted (b) is difficult to remain.

Resin [K6] is a resin in which carboxylic acid anhydride is additionally reacted with resin [K5]. The carboxylic acid anhydride is reacted with a hydroxy group generated by the reaction of the cyclic ether with carboxylic acid or carboxylic acid anhydride.

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- And tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hepto-2-ene anhydride. The amount of carboxylic acid anhydride used is preferably 0.5 to 1 mole relative to 1 mole of (a).

Specifically as the resin (B), 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxycitricyclo[5.2.1.0 ^2,6 ]decyl(meth)acrylate/ Resins such as (meth)acrylic acid copolymers [K1]; Glycidyl(meth)acrylate/benzyl(meth)acrylate/(meth)acrylic acid copolymer, glycidyl(meth)acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2 .1.0 ^2,6 ]decyl(meth)acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl(meth)acrylate/( Resins such as meta)acrylic acid/vinyl toluene copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer [K2]; Resin [K3], such as benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer, benzyl (meth)acrylate/tricyclodecyl (meth)acrylate/(meth)acrylic acid copolymer ]; A resin obtained by adding glycidyl (meth)acrylate to a benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth) to a tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer Resin [K4], such as resin which added acrylate, resin which added glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer; Tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate copolymer of (meth) acrylic acid resin, tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate of Resins such as resins in which (meth)acrylic acid is reacted with a copolymer [K5]; And resins such as a resin [K6] in which tetrahydrophthalic anhydride is reacted with a resin in which (meth)acrylic acid is reacted with a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate. .

The resin (B) is preferably a type selected from the group consisting of resin [K1], resin [K2] and resin [K3], and more preferably selected from the group consisting of resin [K2] and resin [K3]. It is kind. In the case of these resins, the developability of the colored curable resin composition becomes excellent. Resin [K2] is more preferable from the viewpoint of adhesion between the colored pattern and the substrate.

The weight average molecular weight of resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, further preferably 5,000 to 30,000. When the molecular weight is within the above range, the coating film hardness is improved, the residual film ratio is high, the solubility in the unexposed portion of the developer is good, and the resolution of the coloring pattern can be improved.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

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

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and even more preferably 17 to 55% by mass, based on the total amount of solids. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and residual film ratio of the colored pattern tend to be improved.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound capable of polymerizing with an active radical and/or acid generated in the polymerization initiator (D), and there are compounds having a polymerizable ethylenically unsaturated bond, and preferably (meth)acrylic acid ester It is a compound.

Polymeric compounds having one ethylenically unsaturated bond include nonylphenylcarbitolacrylate, 2-hydroxy-3-phenoxypropylacrylate, 2-ethylhexylcarbitolacrylate, 2-hydroxyethylacrylate, N-vinylpyrrolidone and the like, and (a), (b) and (c) described above are also mentioned.

Polymerizable compounds having two ethylenically unsaturated bonds include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di( And meth)acrylate, bis(acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di(meth)acrylate.

Especially, it is preferable that a polymerizable compound (C) is a polymerizable compound which has three or more ethylenically unsaturated bonds. Such polymerizable compounds include trimethylol propane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(metha) )Acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona (meth)acrylate, tris(2-(meth) )Acryloyloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene Glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like, and dipentaerythritol is preferred. And penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

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

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

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

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

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating polymerization by generating active radicals, acids, and the like by light and thermal action, and a known polymerization initiator can be used.

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

The O-acyloxime compound is a compound having a structure represented by formula (d1). Hereinafter, * represents a bonding hand.

[Formula 84]

The O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane- 1-on-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl- 6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3- Dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl )-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine and N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3- Il]-3-cyclopentylpropan-1-one-2-imine. You may use commercial items, such as the monovalent OXE01, OXE02 (above, BASF company make), and N-1919 (made by ADEKA company). Among them, O-acyloxime compounds are N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane- At least one member selected from the group consisting of 1-on-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine is preferred, and N -Benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine is more preferable. With these O-acyloxime compounds, a high-brightness color filter can be obtained.

The alkylphenone compound is, for example, a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3).

[Formula 85]

As a compound having a structure represented by formula (d2), 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morph Polynophenyl)-2-benzylbutan-1-one and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1- And the like. You may use commercial items, such as Ilgacure 369, 907, 379 (above, BASF Corporation).

As a compound having a structure represented by formula (d3), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxy Ethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α, α -Diethoxy acetophenone, benzyl dimethyl ketal, and the like.

In terms of sensitivity, a compound having a structure represented by formula (d2) is preferable as the alkylphenone compound.

Examples of the biimidazole compound include compounds represented by formula (d5).

[Formula 86]

[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 phenyl group, tolyl group, xylyl group, ethylphenyl group and naphthyl group, and are preferably phenyl groups.

As a substituent, a halogen atom, a C1-C4 alkoxy group, etc. are mentioned. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and 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 are preferably methoxy groups.

As the biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)- 4,4',5,5'-tetraphenylbiimidazole (See, for example, Japanese Patent Application Laid-Open No. Hei 6-75372, Hei Hei 6-75373, etc.), 2,2'-bis (2-chloro Phenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole , 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4 ',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, Publication No. 48-38403, Publication No. 62-174204, etc.) and 4,4',5,5' And a biimidazole compound in which the phenyl group at the position is substituted by a carboalkoxy group (for example, see Japanese Unexamined Patent Publication No. Hei 7-10913, etc.). Among them, compounds represented by the following formulas and mixtures thereof are preferred.

[Formula 87]

As the triazine compound, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-( 4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(triclo Romethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl) Ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2 ,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine and 2,4-bis(trichloromethyl)- 6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine and the like.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

In addition, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, methyl 2-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone , 2,4,6-trimethylbenzophenone and other benzophenone compounds; Quinone compounds such as 9,10-phenansrenquinone, 2-ethylanthraquinone and campoquinone; And 10-butyl-2-chloroacridone, benzyl, phenylglyoxylic acid methyl ester, and titanocene compounds.

It is preferable to use these in combination with the polymerization start adjuvant (D1) (especially amines) mentioned later.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one member selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds, and more preferably It is a polymerization initiator comprising an O-acyloxime 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 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Is 0.1 to 32 parts by mass, particularly preferably 1 to 30 parts by mass.

<Polymerization start adjuvant (D1)>

The polymerization initiation aid (D1) is a compound or sensitizer used to promote polymerization of the polymerizable compound in which polymerization is initiated by the polymerization initiator. When a polymerization initiator auxiliary (D1) is included, it is generally used in combination with a polymerization initiator (D).

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

The amine compound includes triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoic acid, ethyl 4-dimethylaminobenzoic acid, isoamyl 4-dimethylaminobenzoic acid, 2-dimethylaminoethylbenzoic acid, 2-ethylhexyl 4-dimethylaminobenzoic acid, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly called mihirazketone), 4,4'-bis(diethylamino)benzophenone And 4,4'-bis(ethylmethylamino)benzophenone, and the like, and preferably 4,4'-bis(diethylamino)benzophenone. You may use commercial items, such as EAB-F (made by Hodogaya Chemical Industry Co., Ltd.).

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

The thioxanthone compounds include 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone and 1-chloro-4-propoxy And city oxanthone.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, and chlorophenyl And sulfanyl acetic acid, dichlorophenyl sulfanyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

When using such a polymerization start adjuvant (D1), the content is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Wealth. When 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 be improved.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent generally used in the field may be used. Specifically, an ester solvent (a solvent containing -COO- in a molecule and not containing -O-), an ether solvent (a solvent containing -O- in a molecule and not containing -COO-), an ether ester solvent (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule, not containing -COO-), alcohol solvent (containing OH in the molecule -O-, Solvents that do not contain -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

Ester solvents include methyl lactic acid, ethyl lactic acid, butyl lactic acid, 2-hydroxyisobutanoic acid methyl ester, ethyl acetate, butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionic acid, isopropyl butyric acid, ethyl butyric acid, butyl And butyric acid, methylpyruvic acid, ethylpyruvic acid, propylpyruvic acid, methyl acetoacetic acid, ethyl acetoacetic acid, cyclohexanol acetate and γ-butyrolactone.

Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and 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 methylethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenitol and methylanisole And the like.

Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl-3-methoxypropionic acid, ethyl-3-methoxypropionic acid, methyl-3- Ethoxypropionic acid, ethyl-3-ethoxypropionic acid, methyl-2-methoxypropionic acid, ethyl-2-methoxypropionic acid, propyl-2-methoxypropionic acid, methyl-2-ethoxypropionic acid, ethyl-2-ethoxy Propionic acid, methyl-2-methoxy-2-methylpropionic acid, ethyl-2-ethoxy-2-methylpropionic acid, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate , Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether And acetate.

As a ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclo And pentanone, cyclohexanone, and isophorone.

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

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

Examples of the amide 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, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionic acid, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide and N-methylpyrrolidone are preferred. , Propylene glycol monomethyl ether acetate, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl Acetate, 3-methoxy-1-butanol, methyl-3-methoxypropionic acid. Ethyl 3-ethoxypropionic acid and N-methylpyrrolidone are more preferred.

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

<Leveling agent (H)>

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

Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicon DC3PA, Copper SH7PA, Copper DC11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Copper SH8400 (trade name: Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials, Japan, etc.).

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in a molecule. Specifically, Prorad (registered trademark) FC430, copper FC431 (Sumitomo 3M Co., Ltd.), Megaface (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper F554, copper R30 , Copper RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, copper EF303, copper EF351, copper EF352 (Mitsubishi Material Electronic Chemical Co., Ltd.), sulfron (registered trademark) S381, Copper S382, copper SC101, copper SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Co., Ltd.).

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in a molecule. Specifically, Megaface (registered trademark) R08, copper BL20, copper F475, copper F477 and F443 (made by DIC Corporation) etc. are mentioned.

When the leveling agent (H) is contained, its content is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, more preferably with respect to the total amount of the colored curable resin composition. It is 0.005 mass% or more and 0.07 mass% or less. When the content of the leveling agent (H) is within the above range, the flatness of the color filter can be improved.

<Antioxidant (J)>

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

As the phenolic antioxidant, Irganox 1010 (Irganox 1010: pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Corporation), Ilganox 1076 (Irganox 1076: Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, manufactured by BASF Corporation), Ilganox 1330 (Irganox 1330: 3,3 ',3'',5,5',5''-hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol, BASF Ilganox 3114 (Irganox 3114: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4) ,6(1H,3H,5H)-trione, manufactured by BASF Corporation, Irganox 3790 (Irganox 3790: 1,3,5-tris((4-tert-butyl-3-hydroxy-2,6 -Xylyl)methyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Corporation), Irganox 1035 (Irganox 1035: thiodiethylene bis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Corporation), Ilganox 1135 (Irganox 1135: benzenepropanoic acid, 3,5-bis(1 ,1-Dimethylethyl)-4-hydroxy, C7-C9 side chain alkyl ester, manufactured by BASF Corporation, Ilganox 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)-o-cresol, BASF( Note), Irganox 3125 (Irganox 3125, manufactured by BASF), Irganox 565 (Irganox 565: 2,4-bis(n-octylthio)-6-(4-hydroxy-3',5 '-Di-tert-butylanilino)-1,3,5-triazine, manufactured by BASF Corporation), adekastab AO-80 (adecastab AO-80: 3,9-bis(2-( 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, Made by ADEKA Co., Ltd., Smizer BHT (Sumilizer B) HT, Sumitomo Chemical Co., Ltd.), Sumizer GA-80 (Sumilizer GA-80, Sumitomo Chemical Co., Ltd.), Sumizerizer GS (Sumilizer GS, Sumitomo Chemical Co., Ltd.), Cyanox 1790 (Cyanox 1790 , Cytec Co., Ltd.) and vitamin E (Ezai Co., Ltd. product).

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

The sulfur-based antioxidants include dialkylthiodipropionate compounds such as dilauryl thiodipropionic acid, dimyristyl or distearyl, and polyols such as tetrakis[methylene(3-dodecylthio)propionate]methane. and β-alkyl mercaptopropionic acid ester compounds.

<Other ingredients>

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

<The manufacturing method of a coloring curable resin composition>

The colored curable resin composition 0 of the present invention is a dye solution (A1), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E), and optionally a leveling agent (H), It can be prepared by mixing the polymerization start adjuvant (D1), antioxidant (J) and other components.

The colored curable resin composition 1 of the present invention is a dye solution (A1), a dye (A2), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E), and additionally leveled if necessary It can be prepared by mixing the agent (H), the polymerization initiation aid (D1), the antioxidant (J), and other components.

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

In the case of including the pigment (P), the pigment is preferably mixed with a part or all of the solvent (E) in advance, and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. At this time, part or all of the pigment dispersant and the resin (B) may be blended as necessary. The desired colored curable resin composition can be prepared by mixing the components remaining in the pigment dispersion thus obtained to a predetermined concentration.

It is preferable that the coloring agent (A), such as a dye solution (A1) and a dye (A2), is previously dissolved in a part or all of the solvent (E) to prepare a solution. It is preferable to filter the solution with a filter having a pore size of about 0.01 to 1 μm.

After mixing, it is preferable to filter the colored curable resin composition with a filter having a filter diameter of about 0.01 to 10 μm.

<Production Method of Color Filter>

A photolithography method, an inkjet method, a printing method, etc. are mentioned as a method of manufacturing a colored pattern from the colored curable resin composition of this invention, Preferably a photolithography method is mentioned. The photolithography method is a method of applying the colored curable resin composition to a substrate, drying it to form a colored composition layer, and exposing and developing the colored composition layer through a photomask. In the photolithography method, a colored coating film that is a cured product of the colored composition layer can be formed by not using and/or developing a photomask during exposure. The colored pattern or colored coating thus formed is the color filter of the present invention.

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

As the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass with silica coating on the surface, resin plates such as polycarbonate, methyl polymethacrylate, polyethylene terephthalate, silicon and aluminum on the substrate, Silver, copper/palladium alloy thin films or the like are used. Separate color filter layers, resin layers, transistors, and circuits may be formed on these substrates.

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

First, the colored curable resin composition is applied onto a substrate, and volatile components such as a solvent are removed and dried by heating drying (pre-baking) and/or drying under reduced pressure to obtain a smooth colored composition layer.

As a coating method, a spin coating method, a slit coating method, and a slit and spin coating method are mentioned.

The temperature when heating and drying is preferably 30 to 120, and more preferably 50 to 110. Further, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

When drying under reduced pressure, it is preferable to do it under a pressure of 50 to 150 Pa and in a temperature range of 20 to 25.

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

Next, the coloring composition layer is exposed through a photomask for forming a desired coloring pattern. The pattern on the photomask is not particularly limited, and a pattern is used depending on the intended use.

The light source used for exposure is preferably a light source that emits light having a wavelength of 250 to 450 nm. For example, light having a wavelength of less than 350 nm may be cut out using a filter that cuts this wavelength range, or light may be selectively extracted using a bandpass filter that extracts these wavelength ranges near 436 nm, near 408 nm, and around 365 nm. As a light source, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

It is preferable to use an exposure apparatus such as a mask aligner and a stepper because it is possible to uniformly irradiate parallel light on the entire exposure surface or to accurately align the photomask and the substrate on which the coloring composition layer is formed.

A colored pattern is formed on the substrate by developing the colored composition layer after exposure by contacting it with a developer. By development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. As the developer, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferred. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.

The developing method may be any of a puddling process, a dipping method, and a spraying method. It is also possible to tilt the substrate at any angle during development.

After development, it is preferable to wash with water.

It is preferable to post-bake additionally to the obtained coloring pattern. The post-baking temperature is preferably 150 to 250, more preferably 160 to 235. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

By using the colored curable resin composition of the present invention, a color filter having a particularly high brightness can be produced. The color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic papers, etc.) and solid-state imaging devices.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples, and it is of course possible to perform it by appropriately changing it within a range suitable for the purpose of the top and the bottom. , These are all included in the technical scope of the present invention. In the following description, unless otherwise specified, "parts" means "parts by mass" and "%" means "mass%".

Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited by these examples. The percentages and parts representing the content to the amount used in the examples are based on mass unless otherwise specified.

[Example 1]

Bis(trifluoromethanesulfonyl)imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) 25 parts propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA. Daicel Co., Ltd.) / diacetone alcohol (hereinafter, It is called DAA 450 parts of mixed solvent (hereinafter referred to as mixed solvent A) of KH Neochem Co., Ltd. = 10/90 (weight ratio) was added, stirred at room temperature for 10 minutes, and completely dissolved. 25 parts of the compound represented by formula (I-1) was added and stirred at room temperature for 13 hours. To the obtained solution, 3.2 parts of Celite 535 (manufactured by Hayashi Chemical Co., Ltd.) were added and stirred at room temperature for 1 hour. The obtained solution was filtered through Kiriyama filter paper No. 5C. The obtained filtrate was filtrated under a pressure of 0.05 MPa nitrogen and filtered through a PTFE membrane disc filter PTAW04700 (1 µm), S4422M022Y11 (0.05 µm) (manufactured by Nippon Integrates Co., Ltd.) to obtain 470.0 parts of a dye solution (A1-1). .

[Example 2]

To 25 parts of bis(trifluoromethanesulfonyl)imide lithium (manufactured by Tokyo Chemical Industries, Ltd.), 450 parts of mixed solvent A was added and stirred at room temperature for 10 minutes to completely dissolve. 25 parts of the compound represented by formula (I-119) was added and stirred at room temperature for 13 hours. To the obtained solution, 3.2 parts of Celite 535 (manufactured by Hayashi Chemical Co., Ltd.) were added and stirred at room temperature for 1 hour. The obtained solution was filtered through Kiriyama filter paper No.5B, and the obtained solution was filtered again through Kiriyama filter paper No.5C. The obtained filtrate was filtrated under a pressure of 0.05 MPa nitrogen and filtered through a PTFE membrane disc filter PTAW04700 (1 µm), S4422M022Y11 (0.05 µm) (manufactured by Nippon Integrals Co., Ltd.), to obtain 470.0 parts of a dye solution (A1-2). .

[Example 3]

470 parts of PGMEA (manufactured by Daicel) was added to 5.0 parts of bis(trifluoromethanesulfonyl)imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.), followed by stirring at room temperature for 10 minutes to completely dissolve. 25 parts of the compound represented by formula (I-155) was added and stirred at room temperature for 13 hours. 5.3 parts of Celite 535 (manufactured by Hayashi Chemical Co., Ltd.) was added to the obtained solution, and stirred at room temperature for 1 hour. The obtained solution was filtered again through Kiriyama filter paper No. 5C. The obtained filtrate was filtered through ultra-high molecular weight polyethylene (UPE) membrane disc filter CWUA04700 (1 µm), CWAZ04700 (0.05 µm) (manufactured by Nippon Integris Co., Ltd.) under nitrogen pressure of 0.05 MPa, and a dye solution (A1-3) ) 470.0 parts were obtained.

[Example 4]

To 25 parts of bis(trifluoromethanesulfonyl)imide lithium (manufactured by Tokyo Chemical Industries, Ltd.), 450 parts of mixed solvent A was added and stirred at room temperature for 10 minutes to completely dissolve. 25 parts of the compound represented by formula (I-160) was added, and stirred at room temperature for 13 hours. To the obtained solution, 3.2 parts of Celite 535 (manufactured by Hayashi Chemical Co., Ltd.) were added and stirred at room temperature for 1 hour. The obtained solution was filtered again through Kiriyama filter paper No. 5C. The obtained filtrate was filtered through a PTFE membrane disc filter PTAW04700 (1 µm), S4422M022Y11 (0.05 µm) (manufactured by Nippon Integrals Co., Ltd.) under nitrogen pressure of 0.05 MPa to obtain 470.0 parts of a dye solution (A1-4). .

[Example 5]

To 25 parts of bis(trifluoromethanesulfonyl)imide lithium (manufactured by Tokyo Chemical Industries, Ltd.), 450 parts of mixed solvent A was added and stirred at room temperature for 10 minutes to completely dissolve. 25 parts of the compound represented by formula (I-161) was added and stirred at room temperature for 13 hours. To the obtained solution, 3.2 parts of Celite 535 (manufactured by Hayashi Chemical Co., Ltd.) were added and stirred at room temperature for 1 hour. The obtained solution was filtered again through Kiriyama filter paper No. 5C. The obtained filtrate was filtrated under a pressure of 0.05 MPa nitrogen and filtered through a PTFE membrane disc filter PTAW04700 (1 μm), S4422M022Y11 (0.05 μm) (manufactured by Nippon Integrals Co., Ltd.) to obtain 470.0 parts of a dye solution (A1-5). .

[Example 6]

445.7 parts of mixed solvent A was added to 25 parts of the compound represented by formula (I-1) and stirred at room temperature for 30 minutes to dissolve completely. To the obtained solution, 25 parts of 3-methacryloxypropyl trimethoxysilane (KBM-503: manufactured by Shin-Etsu Chemical Co., Ltd.) was added and stirred at room temperature for 15 hours. 5.3 parts of Celite 535 (manufactured by Hayashi Chemical Co., Ltd.) was added to the resulting solution, and stirred at room temperature for 1 hour. The obtained solution was filtered through Kiriyama filter paper No.5B, and the obtained solution was filtered again through Kiriyama filter paper No.5C. The obtained filtrate was filtered under nitrogen pressure of 0.05 MPa through a PTFE membrane disc filter PTAW04700 (1 µm), S4422M022Y11 (0.05 µm) (manufactured by Nippon Integrase Co., Ltd.) to obtain 485 parts of a dye solution (A1-6).

[Example 7]

470 parts of PGMEA (manufactured by Daicel Co.) was added to 5.0 parts of tris(trifluoromethanesulfonyl)methide lithium (manufactured by Central Glass Co., Ltd.), followed by stirring at room temperature for 10 minutes to completely dissolve. 25 parts of the compound represented by formula (I-155) was added and stirred at room temperature for 13 hours. To the obtained solution, 5.3 parts of Kyowa 700SEN-S (manufactured by Kyowa Chemical Industries, Ltd.) were added and stirred at room temperature for 1 hour. The obtained solution was filtered again through Kiriyama filter paper No. 5C. The obtained filtrate was filtered through ultra-high molecular weight polyethylene (UPE) membrane disc filter CWUA04700 (1 µm), CWAZ04700 (0.05 µm) (manufactured by Nippon Integrals Co., Ltd.) under nitrogen 0.05 MPa pressure, and a dye solution (A1-7) ) 470.0 parts were obtained.

[Example 8]

To 25 parts of bis(trifluoromethanesulfonyl)imide lithium (manufactured by Tokyo Chemical Industries, Ltd.), 450 parts of mixed solvent A was added and stirred at room temperature for 10 minutes to completely dissolve. 25 parts of the compound represented by formula (I-161) was added and stirred at room temperature for 13 hours. 3.2 parts of Kyowa 2000 (manufactured by Kyowa Chemical Industries, Ltd.) were added to the resulting solution, and stirred at room temperature for 1 hour. The obtained solution was filtered again through Kiriyama filter paper No. 5C. The obtained filtrate was filtrated under a pressure of 0.05 MPa nitrogen and filtered through a PTFE membrane disc filter PTAW04700 (1 μm), S4422M022Y11 (0.05 μm) (manufactured by Nippon Integrals Co., Ltd.) to obtain 470.0 parts of a dye solution (A1-8). .

[Example 9]

To 25 parts of bis(trifluoromethanesulfonyl)imide lithium (manufactured by Tokyo Chemical Industries, Ltd.), 450 parts of mixed solvent A was added and stirred at room temperature for 10 minutes to completely dissolve. 25 parts of the compound represented by formula (I-1) was added and stirred at room temperature for 13 hours. To the obtained solution, 3.2 parts of Kyowa 500SH (Kyowa Chemical Industry Co., Ltd.) were added and stirred at room temperature for 1 hour. The obtained solution was filtered again through Kiriyama filter paper No. 5C. The obtained filtrate was filtrated under a pressure of 0.05 MPa nitrogen and filtered through a PTFE membrane disc filter PTAW04700 (1 μm), S4422M022Y11 (0.05 μm) (manufactured by Nippon Integrals Co., Ltd.) to obtain 470.0 parts of a dye solution (A1-9). .

[Example 10]

445.7 parts of mixed solvent A was added to 25 parts of the compound represented by formula (I-1) and stirred at room temperature for 30 minutes to dissolve completely. To the obtained solution, 25 parts of 3-methacryloxypropyl trimethoxysilane (KBM-503: manufactured by Shin-Etsu Chemical Co., Ltd.) was added and stirred at room temperature for 15 hours. 5.3 parts of Kyowa 500SH (manufactured by Kyowa Chemical Industries, Ltd.) was added to the obtained solution, and stirred at room temperature for 1 hour. The obtained solution was filtered through Kiriyama filter paper No.5B, and the obtained solution was filtered again through Kiriyama filter paper No.5C. The obtained filtrate was filtered under a pressure of 0.05 MPa nitrogen and filtered through a PTFE membrane disc filter PTAW04700 (1 μm), S4422M022Y11 (0.05 μm) (manufactured by Nippon Integrals Co., Ltd.) to obtain 485 parts of a dye solution (A1-10).

[Example 11]

450 parts of mixed solvent A was added to 25 parts of bis(3,5-di-tert-butylsalicylic acid) zinc (BONTRON (registered trademark) E-84 (manufactured by Orient Chemical Industries, Ltd.)) and stirred for 10 minutes at room temperature. Dissolve completely. 25 parts of the compound represented by formula (I-161) was added and stirred at room temperature for 13 hours. To the obtained solution, 2 parts of Kyowa 2000 (manufactured by Kyowa Chemical Industries, Ltd.) 3. were added and stirred at room temperature for 1 hour. The obtained solution was filtered again through Kiriyama filter paper No. 5C. The obtained filtrate was filtrated under a pressure of 0.05 MPa nitrogen and filtered through a PTFE membrane disc filter PTAW04700 (1 μm), S4422M022Y11 (0.05 μm) (manufactured by Nippon Integrals Co., Ltd.) to obtain 470.0 parts of a dye solution (A1-11). .

[Comparative Example 1]

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

[Comparative Example 2]

25 parts of the compound represented by formula (I-1) was added to 475 parts of mixed solvent A, stirred for 15 hours at room temperature, and 5.3 parts of Celite (made by Hayashi Pharmaceutical Co., Ltd.) were added and stirred for 1 hour at room temperature. . The obtained solution was filtered through Kiriyama filter paper No.5B, and the obtained solution was filtered again through Kiriyama filter paper No.5C. The obtained filtrate was filtered under a pressure of 0.05 MPa nitrogen and filtered through a PTFE membrane disc filter PTAW04700 (1 μm), S4422M022Y11 (0.05 μm) (manufactured by Nippon Integrals Co., Ltd.) to obtain 485 parts of a dye solution (A1-R2).

[Comparative Example 3]

25 parts of the compound represented by formula (I-160) was added to 475 parts of mixed solvent A, stirred for 15 hours at room temperature, and 5.3 parts of Celite (made by Hayashi Pharmaceutical Co., Ltd.) were added and stirred for 1 hour at room temperature. . The obtained solution was filtered again through Kiriyama filter paper No. 5C. The obtained filtrate was filtered under a pressure of 0.05 MPa nitrogen and filtered through a PTFE membrane disc filter PTAW04700 (1 μm), S4422M022Y11 (0.05 μm) (manufactured by Nippon Integrals Co., Ltd.) to obtain 485 parts of a dye solution (A1-R3).

[Comparative Example 4]

25 parts of the compound represented by formula (I-161) was added to 475 parts of mixed solvent A, stirred at room temperature for 15 hours, and 5.3 parts of Celite (manufactured by Hayashi Pharmaceutical Co., Ltd.) were added and stirred at room temperature for 1 hour. . The obtained solution was filtered again through Kiriyama filter paper No. 5C. The obtained filtrate was filtered under a pressure of 0.05 MPa nitrogen and filtered through a PTFE membrane disc filter PTAW04700 (1 μm), S4422M022Y11 (0.05 μm) (manufactured by Nippon Integrals Co., Ltd.) to obtain 485 parts of a dye solution (A1-R4).

[Comparative Example 5]

25 parts of the compound represented by formula (I-119) was added to 475 parts of mixed solvent A, stirred for 15 hours at room temperature, and 5.3 parts of Celite (manufactured by Hayashi Pharmaceutical Co., Ltd.) were added and stirred for 1 hour at room temperature. . The resulting solution was treated with Kiriyama filter paper No. Filtered through B, and the obtained solution was filtered again through Kiriyama filter paper No. 5C. The obtained filtrate was filtered under a pressure of 0.05 MPa nitrogen and filtered through a PTFE membrane disc filter PTAW04700 (1 µm), S4422M022Y11 (0.05 µm) (manufactured by Nippon Integrase Co., Ltd.) to obtain 485 parts of a dye solution (A1-R5).

[Comparative Example 6]

25 parts of the compound represented by formula (I-161) was added to 475 parts of mixed solvent A, stirred for 15 hours at room temperature, and 5.3 parts of Kyowa 2000 (Kyowa Chemical Industry Co., Ltd.) were added and stirred for 1 hour at room temperature. Did. The obtained solution was filtered again through Kiriyama filter paper No. 5C. The obtained filtrate was filtered through a PTFE membrane disk filter PTAW04700 (1 µm), S4422M022Y11 (0.05 µm) (manufactured by Nippon Integrals Co., Ltd.) under nitrogen 0.05 MPa pressure to obtain 485 parts of a dye solution (A1-R6).

[Comparative Example 7]

25 parts of the compound represented by formula (I-1) was added to 475 parts of mixed solvent A, stirred for 15 hours at room temperature, and 5.3 parts of Kyowa 500SH (Kyowa Chemical Industry Co., Ltd.) were added and stirred for 1 hour at room temperature. Did. The obtained solution was filtered through Kiriyama filter paper No.5B, and the obtained solution was filtered again through Kiriyama filter paper No.5C. The obtained filtrate was filtered under a pressure of 0.05 MPa nitrogen and filtered through a PTFE membrane disc filter PTAW04700 (1 μm), S4422M022Y11 (0.05 μm) (manufactured by Nippon Integrase Co., Ltd.) to obtain 485 parts of a dye solution (A1-R7).

(Confirmation of stability over time)

Each dye solution obtained in Examples 1 to 6 and Comparative Examples 2 to 5 was stored at temperatures of -20, 10°C, 23, 40, and the presence or absence of precipitates was visually confirmed after one week. Table 1 shows the results. "○" means that the precipitate was not confirmed, and "X" means that the precipitate was confirmed.

According to the method for preparing a dye solution according to the present invention, since a dye solution having excellent stability over time can be prepared, it is possible to suppress the formation of precipitates due to the change over time in the dye solution obtained. The dye solution having excellent stability over time can be prepared with a colored curable resin composition by mixing with a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and efficiently colored using the colored curable resin composition. It becomes possible to manufacture filters and display devices.

Claims (10)

(a) Xanthene dye
(b) a step of stirring at least one selected from the group consisting of salts of organic acids and compounds containing silicon atoms in the presence of an organic solvent; And
After the stirring process, as a method for producing a dye solution that further comprises a solid-liquid separation process,
The organic solvent is a carboxylic acid ester of an alkylene glycol monoalkyl ether, an aliphatic alcohol having a ketone carbonyl group, or a mixed solvent thereof,
The solid-liquid separation process is a method of producing a dye solution that is performed using a filter aid. delete The method according to claim 1, wherein the organic acid is an aliphatic carboxylic acid, aromatic carboxylic acid, aliphatic sulfonic acid, alicyclic sulfonic acid, aromatic sulfonic acid, at least selected from compounds represented by the following formula (h1) and compounds represented by the following formula (h2) Hydrogen atoms other than the acidic protons 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 hydroxy group, and the aliphatic carboxylic acid, the aliphatic sulfonic acid and the -CH ₂ -constituting the alicyclic sulfonic acid is a method for producing a dye solution that can be substituted with -CO-.
[Formula 2]

[In formula (h1), X ^h1 and X ^h2 independently represent a fluorine atom or a C 1-4 fluorinated alkyl group, or X ^h1 and X ^h2 are combined to form a C 2-4 fluorinated alkanediyl group. .
In the formula (h2), X ^h3 to X ^h5 represent, independently of each other, a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms.] The method according to claim 1, wherein the silicon atom-containing compound is a compound represented by the following formula (j).
[Formula 3]

[In formula (j),
R ^h1 represents a hydrogen atom, a hydroxy 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 ^h1s may be the same or different.
R ^h2 is a monovalent substituent, saturated hydrocarbon group having 1 to 10 carbon atoms, aromatic hydrocarbon group having 6 to 10 carbon atoms or vinyl group, epoxy group, methacryl group, acrylic group, amino group, isocyanurate group, ureido group, mer Represents a substituent containing at least one functional group selected from the group consisting of capto groups, sulfide groups and isocyanate groups.] delete The method for producing a dye solution according to claim 1, wherein the xanthene dye is represented by the following formula (1a).
[Formula 4]

[In formula (1a),
R ¹ to R ⁴ are, independently of each other, a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or formula (ii) Indicates the displayed group.
*-R ⁵⁰ -Si(R ²⁹ ) ₃ (ii)
(In 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 may be the same or different.
R ⁵⁰ represents an alkanediyl group having 1 to 10 carbon atoms, and -CH ₂ -constituting the alkanediyl group is -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH- , -NHCOO-, -CONH- or -NHCO-. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.
* Indicates a bond with a nitrogen atom.)
-CH ₂ -contained in the saturated hydrocarbon group of R ¹ to R ⁴ is -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-, R ¹ and R ² together may form a ring containing a nitrogen atom, R ³ and R ⁴ together may form a ring containing a nitrogen atom. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.
R ⁵ is _{^{-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 the integer of 0-5. When m is 2 or more, a plurality of R ^d may be the same or different.
a represents the integer of 0 or 1.
X represents a halogen atom.
Z ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and four R ¹¹ may be the same or different.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R ⁹ and R ¹⁰ each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a substituent, and -CH ₂ -contained in the saturated hydrocarbon group is -O-, -CO-,- NR ¹¹ -, -OCO-, -COO-, -OCONH, -NHCOO-, -CONH- or -NHCO- can be substituted, R ⁹ and R ¹⁰ are bonded to each other of a 3 to 10 membered ring containing a nitrogen atom Hetero rings can be formed. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.
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 solution according to claim 1, wherein the xanthene dye is a compound represented by the following formula (1d).
[Formula 5]

[In formula (1d),
R ^1d to R ^4d are, independently of each other, a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or formula (ii) It represents a group represented, and at least one of R ^1d to R ^4d is a group represented by formula (ii).
*-R ⁵⁰ -Si(R ²⁹ ) ₃ (ii)
(In 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 may be the same or different.
R ⁵⁰ represents an alkanediyl group having 1 to 10 carbon atoms, and -CH ₂ -constituting the alkanediyl group is -O-, -CO-, -NR ^11d -, -OCO-, -COO-, -OCONH- , -NHCOO-, -CONH- or -NHCO-. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.
* Indicates a bond with a nitrogen atom.)
-CH ₂ -contained in the saturated hydrocarbon group of R ^1d to R ^4d is -O-, -CO-, -NR ^11d -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-, R ^1d and R ^2d together may form a ring containing a nitrogen atom, and R ^3d and R ^4d together may form a ring containing a nitrogen atom. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.
R ^5d is _{^{-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 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
md represents the integer of 0-5. When md is 2 or more, a plurality of R ^5ds may be the same or different.
d represents the integer of 0 or 1.
Xd represents a halogen atom.
Zd ⁺ represents ⁺ N(R ^11d ) ₄ , Na ⁺ or K ⁺ , and the four R ^11ds may be the same or different.
R ^8d represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R ^9d and R ^10d represent, independently of each other, a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and -CH ₂ -contained in the saturated hydrocarbon group is -O-, -CO-,- NR ^11d -, -OCO-, -COO-, -OCONH, -NHCOO-, -CONH- or -NHCO- can be substituted, and R ^9d and R ^10d are bonded to each other to form a 3 to 10-membered ring containing a nitrogen atom. Hetero rings can be formed. However, adjacent -CH ₂ -is not simultaneously substituted by the same group, and the terminal -CH ₂ -may not be substituted.
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.] A colored curable resin composition comprising a dye solution prepared by any one of claims 1, 3, 4, 6, and 7 and a resin (B), a polymerizable compound (C), and a polymerization initiator (D). . A color filter formed of the colored curable resin composition according to claim 8. A display device comprising the color filter according to claim 9.