KR102509937B1 - Colored curable resin composition - Google Patents

Abstract

containing a colorant, a resin, a polymerizable compound and a polymerization initiator;
The colorant is a colored curable resin composition comprising a triarylmethane colorant, a xanthene dye, and an anthraquinone dye.

Description

Colored curable resin composition {COLORED CURABLE RESIN COMPOSITION}

The present invention relates to a colored curable resin composition.

As a colored curable resin composition for forming a color filter contained in a liquid crystal display device or the like or a solid-state imaging device, Japanese Patent Application Laid-Open No. 2015-199912, coloring containing a triarylmethane dye and a xanthene dye as a colorant A curable resin composition is described.

The present invention provides the following [1] to [5].

[1] containing a colorant, a resin, a polymerizable compound and a polymerization initiator,

The colorant is a colored curable resin composition comprising a triarylmethane colorant, a xanthene dye, and an anthraquinone dye.

[2] The colored curable resin composition according to [1], wherein the content of the anthraquinone dye is 0.5 to 50 parts by mass based on 100 parts by mass of the triarylmethane colorant.

[3] The colored curable resin composition according to [2], wherein the content of the anthraquinone dye is 1.0 to 13.5 parts by mass based on 100 parts by mass of the triarylmethane colorant.

[4] A color filter formed from the colored curable resin composition according to any one of [1] to [3].

[5] A display device including the color filter according to [4].

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). The colored curable resin composition of the present invention preferably contains a solvent (E) and/or a leveling agent (F), and may further contain an antioxidant (H) and other components. The colorant (A) includes a triarylmethane colorant (Aa1), a xanthene dye (Aa2) and an anthraquinone dye (Aa3). Since the colored curable resin composition of this invention has the said structure, a high-contrast color filter can be manufactured.

<Colorant (A)>

The colorant (A) includes a triarylmethane colorant (Aa1), a xanthene dye (Aa2) and an anthraquinone dye (Aa3). A dye different from the triarylmethane colorant (Aa1), the xanthene dye (Aa2), and the anthraquinone dye (Aa3) (hereinafter sometimes referred to as “dye (Aa4)”) may also be included.

(triarylmethane colorant (Aa1))

The triarylmethane colorant (Aa1) is a colorant containing a compound having a triarylmethane skeleton in a molecule. As the coloring agent, dyes and pigments are exemplified, and a laked pigment may be used. As the triarylmethane colorant (Aa1), a dye containing a compound represented by formula (A-I) and a tautomer thereof (hereinafter, these may be collectively referred to as "compound (A-I)") is preferable. do.

When using Compound (A-I), the content of Compound (A-I) in the triarylmethane colorant (Aa1) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably is 90% by mass or more. Especially, it is preferable to use only compound (A-I) as a triarylmethane colorant (Aa1).

[In Formula (A-I), [Y ² ] ^m- represents an m-valent anion.

R ⁴¹ to R ⁴⁴ are, independently of each other, a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted, a group in which oxygen atoms are inserted between carbon atoms constituting an alkyl group having 2 to 20 carbon atoms, which may be substituted; An aryl group or an aralkyl group which may be substituted is shown. R ⁴¹ and R ⁴² may be bonded together to form a ring with the nitrogen atom to which they are bonded, or R ⁴³ and R ⁴⁴ may be bonded together with the nitrogen atom to which they are bonded to form a ring.

R ⁴⁵ to ^{R 52} are each independently a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms, or an oxygen atom inserted between carbon atoms constituting an alkyl group having 2 to 8 carbon atoms, group, or R ⁴⁶ and R ⁵⁰ may be bonded to each other to form -O-, -NH-, -S- or -SO ₂ -.

Y ¹ represents an optionally substituted aryl group or an optionally substituted heteroaryl group.

When the compound represented by Formula (A-I) contains a plurality of cations, the plurality of cations may have the same structure or different structures.

m represents any natural number.]

[Y ² ] ^m- represents an m-valent anion. The anion represented by [Y ² ] ^m is not particularly limited as long as it is an anion capable of forming a dye cation and a counter ion, and is preferably a boron-containing anion, an aluminum-containing anion, a fluorine-containing anion, It is a halogen anion such as chlorine anion, and an anion having an oxygen atom and at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus.

As a boron-containing anion and an aluminum-containing anion, the anion represented by Formula (4) is mentioned, for example.

[In Formula (4), W ¹ and W ² each independently represent a group obtained by releasing a proton from a compound having two monovalent proton-donating substituents. M represents boron or aluminum.]

Regarding formula (4), examples of the compound having two monovalent proton-donating substituents include compounds having two monovalent proton-donating substituents (eg, hydroxy group, carboxy group, etc.). For example, di Hydroxynaphthalene, optionally substituent 2,2'-biphenol, optionally substituent 3-hydroxy-2-naphthoic acid, optionally substituent 2-hydroxy-1-naphthoic acid , 1-hydroxy-2-naphthoic acid which may have a substituent, binaphthol which may have a substituent, salicylic acid which may have a substituent, benzilic acid which may have a substituent, or mandelic acid which may have a substituent. can

The group in which protons are released from the compound means a group in which protons are all dissociated from a plurality of proton-donating substituents in the compound and have O ^- or COO ^- .

As the compound, catechol which may have a substituent, 2,3-dihydroxynaphthalene which may have a substituent, 2,2'-biphenol which may have a substituent, 3-hydroxy-2 which may have a substituent -Naphthoic acid, 2-hydroxy-1-naphthoic acid which may have a substituent, 1-hydroxy-2-naphthoic acid which may have a substituent, binaphthol which may have a substituent, substituent It is preferable that it is salicylic acid which may have, benzilic acid which may have a substituent, or mandelic acid which may have a substituent.

In each of the above compounds, examples of the substituent include a saturated hydrocarbon group (such as an alkyl group and a cycloalkyl group), a halogen atom, a hydroxyl group, an amino group, a nitro group, and an alkoxy group.

As salicylic acid which may have a substituent, salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-methoxysalicylic acid, 3-nitrosalicylic acid, 4-trifluoromethylsalicylic acid, 3,5-di-tert-butyl monoaminosalicylic acids such as salicylic acid, 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, and 6-aminosalicylic acid; 3-hydroxysalicylic acid (2,3-dihydroxybenzoic acid), 4-hydroxysalicylic acid (2,4-dihydroxybenzoic acid), 5-hydroxysalicylic acid (2,5-dihydroxybenzoic acid), 6- monohydroxysalicylic acids such as hydroxysalicylic acid (2,6-dihydroxybenzoic acid); dihydroxysalicylic acids such as 4,5-dihydroxysalicylic acid and 4,6-dihydroxysalicylic acid; monohalosalicylic acids such as 3-chlorosalicylic acid, 4-chlorosalicylic acid, 5-chlorosalicylic acid, 6-chlorosalicylic acid, 3-bromosalicylic acid, 4-bromosalicylic acid, 5-bromosalicylic acid, and 6-bromosalicylic acid; dihalosalicylic acids such as 3,5-dichlorosalicylic acid, 3,5-dibromosalicylic acid, and 3,5-diiodosalicylic acid; trihalosalicylic acids such as 3,5,6-trichlorosalicylic acid; etc. can be mentioned.

As benzilic acid which may have a substituent, the compound etc. represented by the following structural formula are mentioned.

Examples of the mandelic acid which may have a substituent include compounds represented by the following structural formulas.

As the anion represented by formula (4), preferably, an anion represented by the following formula is an anion (BC-1) to anion (BC-24) having a substituent described in Table 1, and each Anions (BC-25) to (BC-28) represented by formula (BC-25), formula (BC-26), formula (BC-27) and formula (BC-28), etc. are exemplified. .

[Wherein, M represents boron or aluminum.]

[In formula (BC-25), M represents boron or aluminum.]

[In formula (BC-26), M represents boron or aluminum.]

[In formula (BC-27), M represents boron or aluminum.]

[In formula (BC-28), M represents boron or aluminum.]

Examples of the anion represented by formula (4) include anion (BC-1), anion (BC-2), anion (BC-3), anion (BC-25), and anion (BC-26) , Anion (BC-27) is preferred, anion (BC-1), anion (BC-2) and anion (BC-25) are more preferred, anion (BC-1), anion (BC-2) is more preferred. Compounds represented by formula (A-I) having any of these anions tend to have excellent solubility in organic solvents.

Examples of the fluorine-containing anion include groups represented by formulas (6), (7), (8) and (9).

[In formula (6), W ³ and W ⁴ each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or W ³ and W ⁴ are combined to represent a fluorinated egg having 1 to 4 carbon atoms. Represents a candiyl group.]

[In Formula (7), W ⁵ , W ⁶ and W ⁷ each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms.]

[In Formula (8), Y ^a represents a fluorinated alkanediyl group having 1 to 4 carbon atoms.]

[In formula (9), Y ^b represents a fluorinated alkyl group having 1 to 4 carbon atoms.]

In the formulas (6), (7) and (9), as the fluorinated alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group is preferable. As the perfluoroalkyl group, -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF 3 , -CF(CF _{3 ) 2} , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF(CF ₃ ) ₂ or -C(CF ₃ ) ₃ .

In the formulas (6) and (8), the fluorinated alkanediyl group having 1 to 4 carbon atoms includes a perfluoroalkanediyl group, and -CF ₂ -, -CF ₂ CF ₂ -, -CF ₂ CF are preferred. ₂ CF ₂ -, -C(CF ₃ ) ₂ -, -CF ₂ CF ₂ CF ₂ CF ₂ -, and the like.

As an anion represented by formula (6) (hereinafter sometimes referred to as “anion (6)”), an anion represented by formulas (6-1) to (6-6) (hereinafter referred to as “anion (6)”) may be referred to as "on (6-1)" to "anion (6-6)").

Examples of the anion represented by formula (7) (hereinafter sometimes referred to as "anion (7)") include anion (7-1) represented by the following formula.

As an anion represented by formula (8) (hereinafter sometimes referred to as “anion (8)”), an anion represented by formulas (8-1) to (8-4) (hereinafter referred to as “anion (8)”) (8-1)” to “anion (8-4)”).

As an anion represented by formula (9) (hereinafter sometimes referred to as “anion (9)”), an anion represented by formulas (9-1) to (9-4) (hereinafter referred to as “anion (9)”) (9-1)” to “anion (9-4)”).

[Y ² ] ^m- is preferably a fluorine-containing anion or polyacid anion, and an anion represented by formula (6), [PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , [SiW ₁₂ O ₄₀ ] ^4- and [W ₁₀ O ₃₂ ] ^4- are more preferable, and anions represented by formulas (6-1) to (6-5), [PW ₁₂ O ₄₀ ] ^3- and [P ₂ W ₁₈ O ₆₂ ] ^6- is more preferable, and an anion represented by formula (6-2) and [PW ₁₂ O ₄₀ ] ^3- are particularly preferable.

m represents an arbitrary natural number, and is equal to the negative charge of the anion [Y ² ] ^m- . m on the cation side is determined so that the charge of the anion [Y ² ] ^m- and the cation are the same. m is preferably a natural number of 1 to 10.

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴¹ to ^{R 44} may be linear, branched or cyclic. The number of carbon atoms in the saturated hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6, and particularly preferably 1 to 4.

Examples of the straight-chain or branched-chain saturated hydrocarbon group include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, and decyl; Branched-chain alkyl groups, such as an isopropyl group, an isobutyl group, and 2-ethylhexyl group, are mentioned. The number of carbon atoms of the linear or branched saturated hydrocarbon is preferably 1 to 8, more preferably 1 to 6, still more preferably 1 to 4.

The cyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group. The number of carbon atoms in the saturated cyclic hydrocarbon group is preferably 3 to 10, more preferably 6 to 10.

The hydrogen atom of the saturated hydrocarbon group of R ⁴¹ to ^{R 44} may be substituted with a substituent. As the said substituent, a substituted or unsubstituted amino group or a halogen atom is mentioned. As a substituted amino group, dialkylamino groups, such as a dimethylamino group, etc. are mentioned, As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Examples of the saturated hydrocarbon group in which a hydrogen atom is substituted with a substituted or unsubstituted amino group or a halogen atom include groups represented by the following formula. In the following formula, * represents a bond with a nitrogen atom.

Among the groups represented by R ⁴¹ to ^{R 44} , examples of groups in which an oxygen atom is inserted between methylene groups (carbon atoms) constituting an alkyl group having 2 to 20 carbon atoms include groups represented by the following formula. In the following formula, * represents a bond with a nitrogen atom. Especially, as a group in which an oxygen atom is inserted between the methylene groups constituting the alkyl group, a group having 2 to 10 carbon atoms is preferable, and a group having 2 to 6 carbon atoms is more preferable. The alkyl group into which an oxygen atom is inserted is preferably a straight-chain alkyl group. Moreover, 1-4 are preferable and, as for carbon number between oxygen atoms, 2-3 are more preferable.

In R ⁴¹ to ^{R 44} , the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, and the aralkyl group has preferably 7 to 20 carbon atoms, more preferably 7 to 10 carbon atoms. It is 10.

Examples of the aryl group for R ⁴¹ to ^{R 44} include a phenyl group, a naphthyl group, and a toluyl group.

Examples of the aryl group in the aralkyl group of R ⁴¹ to ^{R 44} include a phenyl group and a naphthyl group, and examples of the aralkyl group include a group in which a bond of such an aryl group and an alkanediyl group are bonded. The alkanediyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and is preferably a linear alkanediyl group. Specific examples of the alkanediyl group include a methylene group, ethylene group, propylene group, butanediyl group, and pentanediyl group, and examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, and the like. can

Among the groups represented by R ⁴¹ to ^{R 44} , as substituents in the aryl group and the aralkyl group, halogen atoms such as fluorine atom, chlorine atom and iodine atom; alkoxy groups having 1 to 6 carbon atoms, such as a methoxy group and an ethoxy group; hydroxy group; C1-C6 alkylsulfonyl groups, such as a methylsulfonyl group; alkoxycarbonyl groups having 2 to 6 carbon atoms, such as a methoxycarbonyl group and an ethoxycarbonyl group; etc. can be mentioned.

As a specific example of the aryl group which may be substituted, the group represented by the following formula is mentioned. In the following formula, * represents a bond with a nitrogen atom.

As an aralkyl group which may be substituted, the group which the alkylene group, such as a methylene group and an ethylene group, couple|bonded with the said aryl group bond is mentioned.

Examples of the ring formed by bonding of R ⁴¹ and R ⁴² together with the nitrogen atom to which they are bonded and the ring formed by bonding of R ⁴³ and R ⁴⁴ together with the nitrogen atom to which they are bonded include a 5-membered ring such as a pyrrolidine ring; Six-membered rings, such as a morpholine ring, a piperidine ring, and a piperazine ring; etc. can be mentioned.

From the viewpoint of ease of synthesis, R ⁴¹ to ^{R 44} are each independently preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aryl group, or an optionally substituted aralkyl group, More preferably, independently of each other, a saturated hydrocarbon group having 1 to 8 carbon atoms or a group represented by the following formula. In the following formula, * represents a bond with a nitrogen atom.

The saturated hydrocarbon group represented by R ⁴⁵ to ^{R 52} may be linear, branched or cyclic, preferably a chain. Examples of the saturated hydrocarbon group represented by R ⁴⁵ to ^{R 52} include groups having 1 to 8 carbon atoms among the groups exemplified as the saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁴ .

As a group in which an oxygen atom is inserted between the methylene groups (carbon atoms) constituting the alkyl group, an alkyl group having 2 to 8 carbon atoms is more preferable. The alkyl group into which an oxygen atom is inserted is preferably a straight-chain alkyl group, and the number of carbon atoms between oxygen atoms is preferably 1 to 4, more preferably 2 to 3. For example, groups represented by the following formulas are exemplified. In the following formula, * represents a bond with a carbon atom.

From the viewpoint of ease of synthesis, R ⁴⁵ to ^{R 52} are preferably each independently a hydrogen atom, a halogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms, and each independently a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom is more preferable.

R ⁴⁶ and R ⁵⁰ may be bonded to each other to form -O-, -NH-, -S- or -SO ₂ -.

Y ¹ represents an optionally substituted aryl group or an optionally substituted heteroaryl group.

The aryl group may be either monocyclic or condensed, and includes aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenyl, tolyl, xylyl, naphthyl, anthryl, phenanthryl, biphenyl and terphenyl. can

The heteroaryl group is a substituent derived from an aromatic heterocycle. The aromatic heterocycle may be either a monocyclic ring or a condensed ring, preferably a 5- to 10-membered ring, and more preferably a 5- to 9-membered ring.

Examples of monocyclic aromatic heterocycles include 5-membered rings having a nitrogen atom such as a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, and a thiazole ring;

5-membered rings having an oxygen atom or a sulfur atom, such as a furan ring and a thiophene ring;

6-membered rings having nitrogen atoms such as pyridine rings, pyrimidine rings, pyridazine rings, and pyrazine rings; etc. can be mentioned. Examples of the condensed-ring aromatic heterocycle include condensed rings having nitrogen atoms such as an indole ring, a benzoimidazole ring, a benzothiazole ring, and a quinoline ring;

rings having an oxygen atom or a sulfur atom, such as a benzofuran ring; etc. can be mentioned. As the heteroaryl group which may be substituted, a group represented by formula (Ab2-x1) is more preferable.

[Ring T ² represents an aromatic heterocycle.

R ⁵³ and R ⁵⁴ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted, a group in which oxygen atoms are inserted between carbon atoms constituting an alkyl group having 2 to 20 carbon atoms, an aryl group which may be substituted, Or an aralkyl group which may be substituted, or a hydrogen atom.

R ⁵⁵ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aryl group.

k1 represents 0 or 1.

* represents a bond with a carbocation.]

Ring T ² represents an aromatic heterocycle, preferably an aromatic heterocycle having 2 to 9 carbon atoms.

In addition, details of R ⁵³ to ^{R 55} are described later.

As the compound (A-I), a compound represented by the formula (A-II) is more preferable.

[In Formula (A-II), [Y ² ] ^m- , R ⁴¹ to ^{R 52} and m are the same as above.

R ⁵³ and R ⁵⁴ are, independently of each other, a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, a group in which oxygen atoms are inserted between carbon atoms constituting an alkyl group having 2 to 20 carbon atoms, and an optionally substituted group. An aryl group or an aralkyl group which may be substituted is shown. R ⁵⁵ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aryl group.

X represents an oxygen atom, -NR ⁵⁷ - or a sulfur atom.

R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

When the compound represented by formula (A-II) contains a plurality of cations, the plurality of cations may have the same structure or different structures.]

Examples of R ⁵³ and R ⁵⁴ include the same groups as those exemplified for R ⁴¹ to R ⁴⁴ .

Examples of the saturated hydrocarbon group of 1 to 20 carbon atoms represented by R ⁵⁵ include the same groups as those exemplified as the saturated hydrocarbon group of R ⁴¹ to R ⁴⁴ . Especially, a C1-C10 alkyl group is preferable, a C1-C8 alkyl group is more preferable, a C1-C6 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.

Examples of the group represented by R ⁵⁵ in which an oxygen atom is inserted between carbon atoms constituting the alkyl group include the same groups as those exemplified for R ⁴¹ to R ⁴⁴ . The alkyl group into which an oxygen atom is inserted is preferably a straight-chain alkyl group. Moreover, 1-4 are preferable and, as for carbon number between oxygen atoms, 2-3 are more preferable.

In R ⁵⁵ , the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms. Examples of the aryl group include the same groups as the aryl groups exemplified for R ⁴¹ to R ⁴⁴ , and a phenyl group is preferable.

Examples of the substituent in the aryl group for R ⁵⁵ include halogen atoms such as a fluorine atom, a chlorine atom, and an iodine atom; alkoxy groups having 1 to 6 carbon atoms, such as a methoxy group and an ethoxy group; hydroxy group; sulfamoil group; C1-C6 alkylsulfonyl groups, such as a methylsulfonyl group; alkoxycarbonyl groups having 2 to 6 carbon atoms, such as a methoxycarbonyl group and an ethoxycarbonyl group; etc. can be mentioned.

From the viewpoint of ease of synthesis, R ⁵⁵ is preferably a saturated hydrocarbon group having 1 to 10 carbon atoms or an optionally substituted aryl group, more preferably an alkyl group having 1 to 8 carbon atoms, or a halogen atom or 1 to 1 carbon atoms. It is an aryl group which may be substituted by the alkoxy group of 4, the hydroxyl group, or the methylsulfonyl group, More preferably, it is a group represented by the following formula. In the following formula, * represents a bond with a carbon atom.

R ⁵⁷ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

X represents an oxygen atom, -NR ⁵⁷ - or a sulfur atom. As a cyclic structure containing X, the group represented by the following formula is mentioned, for example. In the formula, R ⁵³ to R ⁵⁵ have the same definitions as above, and * represents a bond with a carbocation. Especially, as X, an oxygen atom or a sulfur atom is preferable, and a sulfur atom is more preferable.

As a cation which formula (A-I) has, cation 1 - cation 27 which have the substituent shown in Table 2 as a cation represented by formula (A-I-1) is mentioned.

In Table 2, Ph1 to Ph12 mean groups represented by the following formula.

As a cation in Formula (A-I), cation 1 - cation 6, cation 11, and cation 12 are preferable, and cation 1, cation 2, and cation 12 are more preferable.

When the compound represented by formula (A-II) contains a plurality of cations, the plurality of cations may have the same structure or different structures.

(xanthene dye (Aa2))

The xanthene dye (Aa2) is a dye containing a compound having a xanthene skeleton in its molecule. As the xanthene dye (Aa2), C.I. Acid Red 51 (hereinafter, the description of C.I. Acid Red is omitted, and only the number is used. Others are the same.), 52, 87, 92, 94, 289, 388, C.I. Acid Violet 9, 30, 102, C.I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. Basic Red 10 (Rhodamine B), 11, C.I. Basic Violet 10, 11, 25, C.I. Solvent Red 218, C.I. Mordant Red 27, C.I. Reactive Red 36 (Rose Bengal B), sulforhodamine G, the xanthene dye described in Japanese Unexamined Patent Publication No. 2010-32999, the xanthene dye described in Japanese Patent No. 4492760, and the like. Especially, a xanthene dye soluble in an organic solvent is preferable.

Among these, as xanthene dye (Aa2), a dye containing a compound represented by formula (1a) and its tautomer (hereinafter, these may be collectively referred to as "compound (1a)") is preferable. When using the compound (1a), the content of the compound (1a) in the xanthene dye (A2) is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. Especially, it is preferable to use only compound (1a) as a xanthene dye (A2).

[In formula (1a), R ¹ to ^{R 4} each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent; The hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms. -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -O-, -CO- or -NR ¹¹ -. R ¹ and R ² together may form a ring containing a nitrogen atom, and R ³ and R ⁴ may form a ring containing a nitrogen atom together.

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 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

m represents an integer of 0 to 5; When m is an integer of 2 or greater, a plurality of R ⁵ 's may be the same or different.

a represents an integer of 0 or 1;

X0 represents a halogen atom.

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

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

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- , -NH- or -NR ⁸ -, and R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom.

⁺ Four R ^11s in N(R ¹¹ ) ₄ independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.]

Examples of the monovalent aromatic hydrocarbon group representing R ¹ to ^{R 4} include a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group and a butylphenyl group.

As the substituent the aromatic hydrocarbon group may have, a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^{-Z +} , -CO ₂ H, -CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ . Among these, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^{-Z +} and -SO ₂ NR ⁹ R ¹⁰ are preferable as substituents, and -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ are more preferable. do. As -SO ₃ ^{-Z +} in this case, -SO ₃ ^-+ N(R ¹¹ ) ₄ is preferable. When R ¹ to ^{R 4} are such groups, a color filter with less generation of foreign matter and excellent heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (1a).

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

Examples of the monovalent saturated hydrocarbon group represented by R ⁸ to ^{R 11} include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a hexadecyl group, an eco straight-chain alkyl groups such as practical groups; branched chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group; and an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group.

Examples of -OR ⁸ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group and an icosyloxy group.

Examples of -CO ₂ R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group and an icosyloxycarbonyl group.

Examples of -SR ⁸ include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group and an icosylsulfanyl group.

As _-SO2R8 , ^a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, an icosylsulfonyl group, etc. are mentioned.

Examples of -SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group and an icosyloxysulfonyl group.

-SO ₂ NR ⁹ R ¹⁰ is a sulfamoyl group;

N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butyl alcohol Pamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl 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)sulfamoyl group diyl group, 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-dimethyl)hexylsulfamoyl 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 a N,N-tert-butylmethylsulfamoyl group, a N,N-butylethylsulfamoyl group, a N,N-bis(1-methylpropyl)sulfamoyl group, a N,N-heptylmethylsulfamoyl group, An N-2 substituted sulfamoyl group etc. are mentioned.

Examples of the substituent in the monovalent saturated hydrocarbon group represented by R ⁹ or R ¹⁰ include a hydroxyl group and a halogen atom.

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

As m, 1-4 are preferable and 1 or 2 is more preferable.

Examples of the C1-C6 alkyl group representing R ⁶ and R ⁷ may be straight-chain or branched-chain, and include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

Examples of the aralkyl group representing R ¹¹ include a benzyl group, a phenylethyl group, and a phenylbutyl group.

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

As the above ⁺ N(R ¹¹ ) ₄ , it is preferable that at least two of the four R ^11s are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. 20-80 are preferable and, as for the total number of carbon atoms of four R ^<11> , 20-60 are more preferable. When ⁺ N(R ¹¹ ) ₄ exists in compound (1a), if R ¹¹ is such a group, a color filter with few foreign substances can be formed from the colored curable resin composition of the present invention containing compound (1a). .

Preferred examples of the compound (1a) include the compound represented by formula (2a) and its tautomers (hereinafter, these are collectively referred to as "compound (2a)"). When using the compound (2a), the content of the compound (2a) in the xanthene dye (A2) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more.

[In formula (2a), R ²¹ to ^{R 24} each independently represent a hydrogen atom, —R ²⁶ , or an aromatic hydrocarbon group which may have a monovalent substituent having 6 to 10 carbon atoms and which may have a substituent. R ²¹ and R ²² together may form a ring containing a nitrogen atom, and R ²³ and R ²⁴ may form a ring containing a nitrogen atom together.

R ²⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ ^{-Z1 +} or -SO ₂ NHR ²⁶ .

m1 represents an integer of 0 to 5. When m1 is an integer greater than or equal to 2, a plurality of R ²⁵ may be the same or different.

a1 represents an integer of 0 or 1.

X1 represents a halogen atom.

R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

Z1 ⁺ represents ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ .

⁺ ₄ R ²⁷ in N(R ²⁷ ) 4 independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group.]

Examples of the monovalent aromatic hydrocarbon group represented by R ²¹ to ^{R 24} include the same groups as those mentioned above as the aromatic hydrocarbon group in R ¹ to R ⁴ . The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with -SO ₃ ^- , -SO ₃ H, -SO ₃ ^{-Z1 +} , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ .

As a combination of R ²¹ to ^{R 24} , R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon groups are -SO ₃ ^- ; It is preferably substituted with -SO ₃ H, -SO ₃ ^{-Z1 +} , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ . In a more preferred combination, R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon groups are -SO ₃ ^- Z1 ⁺ or -SO ₂ NHR ²⁶ is substituted.

When R ²¹ to ^{R 24} are such groups, a color filter having excellent heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (2a).

As a ring containing a nitrogen atom formed by R ²¹ and R ²² together and a ring containing a nitrogen atom formed by R ²³ and R ²⁴ taken together, R ¹ and R ² are formed together. Rings similar to the rings are exemplified. Among them, an aliphatic heterocycle is preferable. As the said aliphatic heterocycle, the following ring is mentioned, for example.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms for R ²⁶ and R ²⁷ include the same groups as the saturated hydrocarbon group for R ⁸ to R ¹¹ .

When R ²¹ to ^{R 24} are -R ²⁶ , -R ²⁶ is each independently preferably a methyl group or an ethyl group. As R ²⁶ in -SO ₃ R ²⁶ and -SO ₂ NHR ²⁶ , a branched chain alkyl group having 3 to 20 carbon atoms is preferable, a branched chain alkyl group having 6 to 12 carbon atoms is more preferable, and a 2-ethylhexyl group is further preferred. desirable. If R ²⁶ is such a group, a color filter with less generation of foreign matter can be formed from the colored curable resin composition of the present invention containing the compound (2a).

Z1 ⁺ is ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ²⁷ ) ₄ .

As the above ⁺ N(R ²⁷ ) ₄ , it is preferable that at least two of the four R ²⁷ are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. Moreover, 20-80 are preferable and, as for the total number of carbon atoms of 4 ^R27 , 20-60 are more preferable. When compound (2a) has ⁺ N(R ²⁷ ) ₄ , R ²⁷ is such a group. From the colored curable resin composition of the present invention containing compound (2a), a color filter with less generation of foreign matter can be formed.

1-4 are preferable and, as for m1, 1 or 2 is more preferable.

Preferred examples of the compound (1a) include the compound represented by formula (3a) and its tautomers (hereinafter, these are collectively referred to as “compound (3a)”). When using the compound (3a), the content of the compound (3a) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more.

[In Formula (3a), R ³¹ and R ³² independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom. may be substituted, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms, and -CH ₂ - contained in the saturated hydrocarbon group is -O-, -CO- or -NR ¹¹ - may be substituted.

R ³³ and R ³⁴ 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.

R ³¹ and R ³³ may be taken together to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be taken together to form a ring containing a nitrogen atom.

p and q each independently represent an integer of 0 to 5; When p is 2 or more, a plurality of R ³³ may be the same or different, and when q is 2 or more, a plurality of R ³⁴ may be the same or different. R ¹¹ represents the same meaning as above.]

Examples of the monovalent saturated hydrocarbon group for R ³¹ and R ³² include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl; branched chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group; and saturated alicyclic hydrocarbon groups having 3 to 10 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group.

As an aromatic hydrocarbon group which may have as a substituent, the same group as the aromatic hydrocarbon group in R ^<1> is mentioned.

As a C1-C3 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned.

It is preferable that R ³¹ and R ³² are each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

Examples of the C1-C4 alkyl group represented by R ³³ and R ³⁴ include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl and the like.

Examples of the alkyl sulfanyl group having 1 to 4 carbon atoms for R ³³ and R ³⁴ include methyl sulfanyl group, ethyl sulfanyl group, propyl sulfanyl group, butyl sulfanyl group and isopropyl sulfanyl group.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms for R ³³ and R ³⁴ include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl and isopropylsulfonyl groups.

R ³³ and R ³⁴ are preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

As for p and q, an integer of 0 to 2 is preferable, and it is preferable that it is 0 or 1.

Examples of the compound (1a) include compounds represented by formulas (1-1) to (1-42) and formula (1-21'), respectively. In the formula, R ²⁶ represents a monovalent saturated hydrocarbon group of 1 to 20 carbon atoms, preferably a branched chain alkyl group of 6 to 12 carbon atoms, more preferably a 2-ethylhexyl group. Compounds represented by formulas (1-1) to (1-29) and formula (1-21') correspond to compound (2a) and are represented by formulas (1-30) to (1-42). The compound corresponds to compound (3a).

Among these, C.I. Sulfonamide of Acid Red 289, C.I. The quaternary ammonium salt of Acid Red 289, C.I. Sulfonamides of Acid Violet 102 or C.I. The quaternary ammonium salt of Acid Violet 102 is preferred. As such a compound, the compound etc. represented by Formula (1-1) - Formula (1-8), Formula (1-11), and Formula (1-12) are mentioned.

From the viewpoint of excellent solubility in organic solvents, compounds represented by formulas (1-30) to (1-39) are preferable.

The xanthene dye (Aa2) is a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink R-H/C" manufactured by Chugai Kasei Co., Ltd., "Rhodamin 6G" manufactured by Taoka Chemical Industry Co., Ltd.) ) if so. A commercially available xanthene dye may be used as a starting material, and may be synthesized with reference to Japanese Unexamined Patent Publication No. 2010-32999.

(anthraquinone dye (Aa3))

The anthraquinone dye (Aa3) may be a known substance. As the anthraquinone dye (Aa3), for example,

C.I. Solvent Yellow 117 (hereinafter, the description of C.I. Solvent Yellow is omitted and only the number is described.), 163, 167, 189,

C.I. Solvent Orange 77, 86,

C.I. Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247,

C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60,

C.I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59:1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139,

C.I. Solvent Green 3, 28, 29, 32, 33,

C.I. acid red 80,

C.I. Acid Green 25, 27, 28, 41,

C.I. acid violet 34,

C.I. Acid Blue 25, 27, 40, 45, 78, 80, 112

C.I. Disperse Yellow 51,

C.I. Disperse Violet 26, 27,

C.I. Disperse Blue 1, 14, 56, 60,

C.I. direct Blue 40,

C.I. Modernt Red 3, 11,

C.I. Mordant Blue 8

etc. can be mentioned. Anthraquinone dyes are preferably soluble in organic solvents.

The anthraquinone dye is more preferably blue, violet or red.

As the anthraquinone dye (Aa3), a compound represented by formula (1b) (hereinafter sometimes referred to as "compound (1b)") is preferable.

[In Formula (1b), R ⁹¹ and R ⁹² are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, an alicyclic hydrocarbon group having 3 to 10 carbon atoms which may have a substituent, or represents a group represented by formula (1b').]

[In formula (1b'), R ⁹³ is an alkyl group having 1 to 6 carbon atoms, a halogen atom, -SO ₃ H, -CO ₂ H, -CO ₂ R ⁹⁴ , -NHCOR ⁹⁴ , -SO ₃ R ⁹⁴ or -SO ₂ NR ⁹⁴ R ⁹⁵ .

R ⁹⁴ represents a saturated hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, a hydroxy group or an amino group, or an alicyclic hydrocarbon group having 3 to 10 carbon atoms which may be substituted with a halogen atom, a hydroxy group or an amino group.

R ⁹⁵ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms.

r represents an integer of 0 to 5; When r is 2 or more, a plurality of R ⁹³ groups may be the same or different.

X ⁹¹ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.]

When compound (1b) has -SO ₃ H and/or -CO ₂ H, these may form a salt (eg, sodium salt or potassium salt).

Examples of the aliphatic hydrocarbon group represented by R ⁹¹ and R ⁹² include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, sec -C1-C10 alkyl groups, such as a butyl group, tert-butyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group, are mentioned.

As a substituent which such an aliphatic hydrocarbon group may have, a hydroxyl group, a halogen atom, etc. are mentioned.

Examples of the alicyclic hydrocarbon group represented by R ⁹¹ , R ⁹² and R ⁹⁴ include cycloalkyl groups having 3 to 10 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group; can be heard

As a substituent which such an alicyclic hydrocarbon group may have, a hydroxyl group, a halogen atom, etc. are mentioned.

Examples of the alkyl group represented by R ⁹³ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, etc. can be heard

Examples of the saturated hydrocarbon group represented by R ⁹⁴ and R ⁹⁵ include alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl groups. can

Examples of -CO ₂ R ⁹⁴ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group and an icosyloxycarbonyl group.

Examples of -NHCOR ⁹⁴ include N-acetylamino group, N-propanoylamino group, N-butyrylamino group, N-isobutyrylamino group, and N-pivaloylamino group.

Examples of -SO ₃ R ⁹⁴ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group and an icosyloxysulfonyl group.

-SO ₂ NR ⁹⁴ R ⁹⁵ is N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group diyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N-(1-ethylpropyl)sulfamoyl group, N-(1,1-dimethylpropyl) alcohol Pamoyl 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-cyclohexylsulfamoyl group, N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) Sulfamoyl group, N-(3,3-dimethylbutyl)sulfamoyl group, N-heptylsulfamoyl group, N-(1-methylhexyl)sulfamoyl group, N-(1,4-dimethylpentyl)sulfamoyl group , N-octylsulfamoyl group, N-(2-ethylhexyl)sulfamoyl group, N-(1,5-dimethyl)hexylsulfamoyl group, N-(1,1,2,2-tetramethylbutyl) alcohol N-1 substituted sulfamoyl groups such as pamoyl group and N-(5-aminopentyl)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 a N,N-tert-butylmethylsulfamoyl group, a N,N-butylethylsulfamoyl group, a N,N-bis(1-methylpropyl)sulfamoyl group, a N,N-heptylmethylsulfamoyl group, An N-2 substituted sulfamoyl group etc. are mentioned.

Examples of the alkanediyl group represented by X ⁹¹ include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group. , Hexane-1,6-diyl group, ethane-1,1-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-di Diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, etc. are mentioned.

Examples of the compound (1b) include compounds represented by formulas (3-1) to (3-11).

As the anthraquinone dye (Aa3), C.I. Solvent Blue 45 is more preferred. With such an anthraquinone dye, it is possible to form a coating film or pattern with higher contrast, and also to form a coating film or pattern having excellent light resistance with less generation of foreign matter.

(Dye (Aa4))

The dye (Aa4) is not particularly limited as long as it is a dye different from the triarylmethane colorant (Aa1), the xanthene dye (Aa2) and the anthraquinone dye (Aa3). Examples of the dye (Aa4) include dyes such as oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes. Specifically, compounds classified as dyes, that is, other than pigments, in the color index (published by The Society of Dyers and Colourists), and well-known dyes described in dyeing notes (shikisensha) are exemplified. According to the chemical structure, azo dyes, cyanine dyes, phthalocyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and Nitro dye etc. are mentioned. Among 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 125, 130;

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

C.I. Solvent Blue 37, 67, 70, 90;

C.I. Solvent Green 34, 35, etc. C.I. solvent dyes;

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

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 57, 66, 73, 80, 88, 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, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 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 6, 7;

C.I. Acid Blue 18, 29, 59, 60, 70, 72, 74, 82, 87, 92, 102, 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. C.I. such as acid green 58, 63, 65, 80, 104, 105, 106, 109 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 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, 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 dye;

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

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

C.I. Modern Trend Red 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 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. Mordant 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. Mordant Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

C.I. Modernt Blue 2, 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. Mordant dyes; etc. can be mentioned.

(Pigment (Ab))

The colored curable resin composition of the present invention may contain a pigment (Ab). The pigment (Ab) is not particularly limited, and known pigments can be used, and examples thereof include pigments classified as pigments in the color index (published by The Society of Dyers and Colourists).

As the pigment (Ab), C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 , 147, 148, 150, 153, 154, 166, 173, 194, yellow pigments such as 214;

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

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

C.I. blue pigments such as Pigment Blue 15, 15:3, 15:4, 15:6, and 60; C.I. Violet color 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. brown pigments such as Pigment Brown 23 and 25;

C.I. Black pigments, such as Pigment Black 1 and 7, etc. are mentioned.

The pigment (Ab) is preferably a blue pigment, more preferably a phthalocyanine pigment and a dioxazine pigment, still more preferably a C.I. It is at least one kind selected from the group consisting of Pigment Blue 15:6 and Pigment Violet 23.

The pigment (Ab) is, if necessary, rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced therein, graft treatment on the surface of the pigment with a polymer compound, etc., atomization treatment by a sulfuric acid atomization method or the like, or impurities are removed. A cleaning treatment with an organic solvent or water for removal, a treatment for removing ionic impurities by an ion exchange method, and the like may be performed. It is preferable that the particle diameter of each pigment is uniform.

The pigment can be made into a pigment dispersion liquid in a state of being uniformly dispersed in a pigment dispersant solution by containing a pigment dispersant and performing dispersion treatment. The pigment may be subjected to dispersion treatment independently, respectively, or may be subjected to dispersion treatment in a mixture of plural types.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigment dispersants. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersant, as a trade name, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF Co., Ltd.), Aji Spa (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (manufactured by Big Chemie Co., Ltd.), and the like are exemplified.

When using a pigment dispersant, the usage amount is preferably 100 parts by mass or less, and more preferably 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the pigment. When the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.

In this specification, the compounds exemplified as each component can be used alone or in combination of plural types unless otherwise specified.

The content rate of the colorant (A) in the colored curable resin is preferably 5% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and still more preferably, with respect to the total amount of solid content. It is 5 mass % or more and 50 mass % or less. If the content rate of the coloring agent (A) is within the above range, desired spectral and color density can be obtained.

In this specification, the "total amount of solid content" refers to the total amount of components except 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 thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

In the colorant (A), the content of each dye can be appropriately selected according to the desired spectroscopy, but the following ranges are preferable from the viewpoint of being able to form a high-contrast coating film or pattern.

The content of the triarylmethane colorant (Aa1) in the colorant (A) is preferably 0.5% by mass or more and 98% by mass or less, more preferably 61% by mass or more and 97% by mass or less, still more preferably 81% by mass or less. It is mass % or more and 96 mass % or less.

The content of the xanthene dye (Aa2) in the colorant (A) is preferably 0.1% by mass or more and 80% by mass or less, more preferably 0.5% by mass or more and 40% by mass or less, and still more preferably 1 It is mass % or more and 20 mass % or less.

The content of the anthraquinone dye (Aa3) in the colorant (A) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more. The content of the anthraquinone dye (Aa3) is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 10% by mass or less.

In the colorant (A), the content of the anthraquinone dye (Aa3) is preferably 0.5 to 50 parts by mass, more preferably 1.0 to 35 parts by mass, based on 100 parts by mass of the triarylmethane colorant (Aa1), More preferably, it is 1.0 to 13.5 parts by mass, and even more preferably, it is 1.2 to 13.1 parts by mass.

When the content of the anthraquinone dye (Aa3) is within the above range, a higher contrast coating film or pattern can be formed.

<Suji (B)>

Although it does not specifically limit as resin (B), It is preferable that it is alkali-soluble resin (B). Alkali-soluble resin (B) (hereinafter sometimes referred to as “resin (B)”) contains a structural unit derived from at least one monomer (a) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride. It is a copolymer.

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

Resin [K1] at least one kind of monomer (a) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as "(a)"), a cyclic ether structure having 2 to 4 carbon atoms, and ethylenic copolymers of monomers (b) having unsaturated bonds (hereinafter sometimes referred to as "(b)");

Resin [K2] (a) and (b), and monomer (c) copolymerizable with (a) (however, it is different from (a) and (b)) (hereinafter sometimes referred to as “(c)”) ) copolymers;

Resin [K3] Copolymer of (a) and (c);

Resin [K4] Resin obtained by reacting (b) with the copolymer of (a) and (c);

Resin [K5] Resin obtained by reacting (a) with the copolymer of (b) and (c);

Resin [K6] A resin obtained by reacting (a) with the copolymer of (b) and (c) and further reacting with carboxylic acid anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinyl benzoic 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-cyclohexenedicarboxylic acid;

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

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

Unsaturated mono [(meth)acryloyloxyalkyl] of divalent or higher polyhydric carboxylic acids such as succinic acid mono [2-(meth)acryloyloxyethyl] and phthalate mono [2-(meth)acryloyloxyethyl] ester;

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

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

(b) has, for example, 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. refers to a polymeric compound.

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

In this specification, "(meth)acrylic acid" shows at least 1 sort(s) chosen 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), for example, a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer having an oxetanyl group and an ethylenically unsaturated bond (b2) (hereinafter sometimes referred to as "(b2)"), a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), and the like.

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

As (b1-1), glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl Glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α -Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxy) Methyl) 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, 2,4,6-tris(glycidyloxymethyl)styrene, etc. can

As (b1-2), vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl ( meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Co., Ltd.) , the compound represented by formula (II) and the compound represented by formula (III), etc. are mentioned.

[In Formula (II) and Formula (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.]

As a C1-C4 alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- butyl group etc. are mentioned.

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

As R ^a and R ^b , a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are preferably used, and a hydrogen atom and a methyl group are more preferable.

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

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

As a compound represented by formula (II), the compound etc. represented by any of formula (II-1) - formula (II-15) are mentioned. Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15) ) is preferred, and compounds represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) are more preferred.

As a compound represented by formula (III), the compound etc. represented by any of formula (III-1) - formula (III-15) are mentioned. Among them, formula (III-1), formula (III-3), formula (III-5), formula (III-7), formula (III-9) or formula (III-11) to formula (III-15) ) is preferred, and compounds represented by formula (III-1), formula (III-7), formula (III-9) or formula (III-15) are more preferred.

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

As (b2), a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferable. As (b2), 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3 -Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryl Royloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, etc. are mentioned.

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

As (b), it is preferable that it is (b1) from the point which can further improve reliability, such as heat resistance and chemical resistance, of the color filter obtained. Moreover, (b1-2) is more preferable at the point which is excellent in the storage stability of colored curable resin composition.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-Ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl(meth)acrylate (called “dicyclopentanyl (meth)acrylate” as a common name in the art) It is also sometimes referred to as "tricyclodecyl (meth)acrylate"), tricyclo[5.2.1.0 ^2,6 ]decen-8-yl(meth)acrylate (as a common name in the art). It is referred to as "dicyclopentenyl (meth) acrylate"), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate. (meth)acrylic acid esters such as lactate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

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

Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxy ratio Cyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2 -N, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene -2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methyl Bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxy Cicarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxy bicyclo unsaturated compounds such as ccarbonyl)bicyclo[2.2.1]hept-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butylate, N-succinimidyl dicarbonylimide derivatives such as -6-maleimide caproate, 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, acetic acid vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among these, from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyltoluene, benzyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl(meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo[2.2.1]hept-2-ene are preferred.

In the resin [K1], the ratio of the structural units derived from each is, among all the structural units constituting the resin [K1],

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

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

It is desirable that

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

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

is more preferable.

When the ratio of the structural units of the resin [K1] is within the above range, the colored curable resin composition tends to have excellent storage stability, developability when forming a colored pattern, and excellent solvent resistance of the color filter obtained.

The resin [K1] is, for example, the method described in the document "Experimental Methods for Polymer Synthesis" (Otsutaka Yuki, published by Otsutaka Yuki, Chemical Dongin Co., Ltd., 1st edition, 1st edition, issued on March 1, 1972) and the citations described in the document It can be prepared with reference to the literature.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, etc. are put into a reaction vessel, for example, by substituting oxygen with nitrogen to create a deoxidized atmosphere, heating and keeping warm while stirring way can be The polymerization initiator and solvent are not particularly limited, and those commonly used in the field can be used. As a polymerization initiator, for example, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) or organic peroxides (benzoyl peroxide, etc.) ) can be mentioned, and the solvent may be one that dissolves each monomer, and the solvent (E) described below may be used as the solvent (E) of the colored curable resin composition of the present invention.

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

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

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

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

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

It is desirable that

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

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

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

is more preferable.

When the ratio of the structural units of the resin [K2] is within the above range, the colored curable resin composition tends to have excellent storage stability, developability when forming a colored pattern, and excellent solvent resistance, heat resistance and mechanical strength of the resulting color filter. there is

Resin [K2] can be produced, for example, in the same manner as described as the method for producing resin [K1].

In the resin [K3], the ratio of the structural units derived from each is, among all the structural units constituting the resin [K3],

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

structural units derived from (c); 40 to 98 mol%

It is desirable that

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

structural units derived from (c); 50 to 90 mol%

is more preferable.

Resin [K3] can be produced, for example, similarly to the method described as the method for producing resin [K1].

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

First, the copolymer of (a) and (c) is prepared in the same manner as described for the production method of Resin [K1]. In this case, it is preferable that the ratio of the structural units derived from each is the same ratio as that of Resin [K3].

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

Continuing to the preparation of the copolymers of (a) and (c), the atmosphere in the flask was substituted from nitrogen to air, and (b), a catalyst for the reaction of carboxylic acid or carboxylic acid anhydride with a cyclic ether (tris(dimethylaminomethyl) Resin [K4] can be manufactured by putting phenol etc.) and polymerization inhibitors (hydroquinone etc.) etc. into a flask, and reacting at 60-130 degreeC for 1 to 10 hours, for example.

The amount of (b) used is preferably 5 to 80 moles, more preferably 10 to 75 moles per 100 moles of (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 forming a pattern, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the pattern obtained tends to become favorable. Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, as (b) used for resin [K4], (b1) is preferable, and (b1-1) is more preferable.

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

Reaction conditions, such as an addition method and reaction temperature and time, can be appropriately adjusted in consideration of production facilities and calorific value due to polymerization. In addition, similarly to the polymerization conditions, the addition method and reaction temperature can be appropriately adjusted in consideration of manufacturing equipment and the calorific value due to polymerization.

For Resin [K5], as a first step, a copolymer of (b) and (c) is obtained in the same manner as in the production method for Resin [K1] described above. Similarly to the above, the obtained copolymer may be used as a solution after reaction, may be used as a concentrated or diluted solution, or may be used obtained as a solid (powder) by a method such as reprecipitation.

The ratio of the structural units derived from (b) and (c) is relative to the total number of moles of all the structural units constituting the copolymer, respectively,

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

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

It is preferable that

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

structural units derived from (c); 10 to 90 mol%

is more preferable.

Further, 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 production method of resin [K4]. , resin [K5] can be obtained.

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

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

Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6 - Tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. are mentioned. The amount of carboxylic acid anhydride used is preferably 0.5 to 1 mole per 1 mole of (a) used.

As the resin (B), specifically, 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl(meth)acrylate/( resins such as meth)acrylic acid copolymer [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/(meth)acrylic acid/ Resin [K2], such as a vinyltoluene copolymer and 3-methyl-3-(meth)acryloyloxymethyl oxetane/(meth)acrylic acid/styrene copolymer; Resins such as benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer, benzyl (meth)acrylate/tricyclodecyl(meth)acrylate/(meth)acrylic acid copolymer [K3 ]; Resin obtained by adding glycidyl (meth)acrylate to benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate to tricyclodecyl(meth)acrylate/styrene/(meth)acrylic acid copolymer ) Resin [K4], such as resin to which acrylate was added, and resin to which glycidyl (meth)acrylate was added to tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer; A resin made by reacting (meth)acrylic acid with a copolymer of tricyclodecyl(meth)acrylate/glycidyl(meth)acrylate, tricyclodecyl(meth)acrylate/styrene/glycidyl(meth)acrylate Resin [K5], such as resin which made the copolymer react with (meth)acrylic acid; Resin [K6], such as a resin obtained by reacting tetrahydrophthalic anhydride with a resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl(meth)acrylate/glycidyl(meth)acrylate; there is.

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

The weight average molecular weight (Mw) of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 30,000. When the weight average molecular weight (Mw) is within the above range, the hardness of the coating film formed from the colored curable resin composition containing the same is improved, the residual film rate is also high, the solubility in the developing solution of the unexposed area is good, and the resolution of the colored pattern tends to improve.

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

The acid value of Resin (B) is preferably 50 to 170 mg-KOH/g, more preferably 60 to 150 mg-KOH/g, still more preferably 70 to 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be obtained by titrating, for example, using 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, still more preferably 17 to 55% by mass with respect to the total amount of solid content. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and remaining film rate of the colored pattern tend to be improved.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized by active radicals and/or acids generated from the polymerization initiator (D). Examples of the polymerizable compound (C) include compounds having a polymerizable ethylenically unsaturated bond, and a (meth)acrylic acid ester compound is preferred.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone etc., and the above-mentioned (a), (b), and (c) are mentioned.

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

It is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more ethylenically unsaturated bonds. As such a polymerizable compound, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa( meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-( meth)acryloyloxyethyl)isocyanurate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like, among which dipentaerythritol penta ( meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferred.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 to 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, still more preferably 17 to 55% by mass with respect to the total amount of solid content.

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

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

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating active radicals, acids, etc. under the action of light or heat, 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 binding hand.

Examples of the O-acyloxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane- 1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl- 6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3- Dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl )-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3- yl] -3-cyclopentylpropan-1-one-2-imine, etc. are mentioned. You may use commercial items, such as Irgacure OXE01, OXE02 (above, BASF Co., Ltd. product), and N-1919 (Adeka Co., Ltd. product). Among them, the O-acyloxime compound is N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl) At least one selected from the group consisting of octan-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine is preferred. , N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine is more preferred. If it is such an O-acyloxime compound, there exists a tendency for a color filter of high brightness to be obtained.

The alkylphenone compound is a compound having a structure represented by formula (d2) or a structure represented by formula (d3), for example. Among these structures, the benzene ring may have a substituent.

Examples of the compound having a structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino-1-(4-morpholino-1-(4-methylsulfanylphenyl)propan-1-one. Polynophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane-1- can be heard on the back. You may use commercial items, such as Irgacure 369, 907, and 379 (above, BASF Corporation make).

Examples of the compound having a structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1-[4-(2-hydroxyl). Ethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α, α - Diethoxy acetophenone, benzyl dimethyl ketal, etc. are mentioned.

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

The said biimidazole compound is a compound represented by Formula (d5), for example.

[In formula (d5), R ¹³ to ^{R 18} represent an aryl group having 6 to 10 carbon atoms which may have a substituent.]

A phenyl group, a toluyl group, a xylyl group, an ethylphenyl group, a naphthyl group, etc. are mentioned as a C6-C10 aryl group, A phenyl group is mentioned preferably.

As a substituent, a halogen atom, a C1-C4 alkoxy group, etc. are mentioned. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, Preferably a chlorine atom is mentioned. As a C1-C4 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc. are mentioned, Preferably a methoxy group is mentioned.

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 Japanese Unexamined Patent Publication No. 6-75372, Japanese Unexamined Patent Publication No. Hei 6-75373, etc.), 2,2'-bis (2 -Chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (di Alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (Japanese Unexamined Patent Publication No. 48-38403) , Japanese Unexamined Patent Publication No. 62-174204, etc.), an imidazole compound in which the phenyl group at the 4,4',5,5'-position is substituted with a carboalkoxy group (Japanese Unexamined Patent Publication No. 7-10913 No. Publication, etc.) and the like. Among them, compounds represented by the following formula and mixtures thereof are preferred.

As said 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(trichloro) 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, 2,4-bis(trichloromethyl)- 6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine etc. are mentioned.

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

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, o-benzoylmethylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone , benzophenone compounds such as 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like.

These are preferably used in combination with a polymerization initiator (D1) described later (especially an amine compound).

The polymerization initiator (D) is preferably a polymerization initiator containing at least one kind selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and biimidazole compounds, more preferably It is preferably a polymerization initiator comprising an O-acyloxime compound.

The content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass, more preferably 1 to 30 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C).

<Polymerization Initiator (D1)>

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

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

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 4-dimethylamino 2-ethylhexyl benzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4 '-bis(ethylmethylamino)benzophenone etc. are mentioned, Among them, 4,4'-bis(diethylamino)benzophenone is preferable. You may use commercial items, such as EAB-F (made by Hodogaya Chemical Industry Co., Ltd.).

Examples of the alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10- Dibutoxy anthracene, 2-ethyl-9,10-dibutoxy anthracene, etc. are mentioned.

Examples of the thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxy. A citioxanthone etc. are mentioned.

As said carboxylic acid compound, phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chloro Phenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenyl glycine, phenoxy acetic acid, naphthyl thioacetic acid, N-naphthyl glycine, naphthoxy acetic acid, etc. are mentioned.

When using such a polymerization initiator (D1), its 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). is the mass part. When the amount of the polymerization initiator (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to improve.

<Solvent (E)>

The solvent (E) is not particularly limited, and solvents commonly used in the field can be used. As the solvent (E), an ester solvent (a solvent that contains -COO- in the molecule and does not contain -O-), an ether solvent (a solvent that contains -O- and does not contain -COO- in the molecule), Ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and not -COO- in the molecule), alcohol solvents (containing OH in the molecule and , solvents that do not contain -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

As the ester solvent, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

As the ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole and methylanisole etc. can be mentioned.

As the ether ester solvent, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , 3-ethoxyethylpropionate, 2-methoxymethylpropionate, 2-methoxyethylpropionate, 2-methoxypropylpropionate, 2-ethoxymethylpropionate, 2-ethoxyethylpropionate, 2-methoxy-2- Methyl methyl propionate, 2-ethoxy-2-methyl ethyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono propyl 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.

As the ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclo Pentanone, 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 the aromatic hydrocarbon solvent include benzene, toluene, xylene and mesitylene.

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

These solvents may be used independently or may use 2 or more types together.

Among them, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide and N-methyl Pyrrolidone and the like are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1 -butanol, ethyl 3-ethoxypropionate and N-methylpyrrolidone are more preferred.

The content rate of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass with respect to the total amount of the colored curable resin composition. When reduced, 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 within the above range, the flatness when the colored curable resin composition is applied is good, and the color density is not insufficient when the color filter is formed, so the display characteristics tend to be good.

<Leveling agent (F)>

Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicon surfactants having a fluorine atom. These may have a polymeric group in a side chain.

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

As said fluorochemical surfactant, surfactant etc. which have a fluorocarbon chain in a molecule|numerator are mentioned. Specifically, Florad (registered trademark) FC430, same FC431 (made by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, same F171, same F172, same F173, same F177, same F183, same F554, same same R30, RS-718-K (manufactured by DIC Co., Ltd.), Ftop (registered trademark) EF301, same EF303, same EF351, same EF352 (manufactured by Mitsubishi Material Electric Kasei Co., Ltd.), Suffron (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratories, Inc.).

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

When containing a leveling agent (F), the content rate 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, with respect to the total amount of the colored curable resin composition. Preferably they are 0.005 mass % or more and 0.07 mass % or less. When the content rate of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Antioxidant (H)>

It is preferable to use antioxidants individually or in combination of 2 or more types from a viewpoint of improving the heat resistance and light resistance of a coloring agent. The antioxidant is not particularly limited as long as it is an antioxidant generally used industrially, and a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant can be used.

As said phenolic antioxidant, Irganox 1010 (Irganox 1010: pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Co., Ltd.) , Irganox 1076 (Irganox 1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, manufactured by BASF Co., Ltd.), Irganox 1330 (Irganox 1330: 3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p- Cresol, manufactured by BASF Co., Ltd., Irganox 3114 (Irganox 3114: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine -2,4,6(1H,3H,5H)-trion, manufactured by BASF Co., Ltd., Irganox 3790 (Irganox 3790: 1,3,5-tris((4-tert-butyl-3-hydrogen) Roxy-2,6-xylyl)methyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Co., Ltd.), Irganox 1035 (Irganox 1035: Thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Co., Ltd., Irganox 1135 (Irganox 1135: benzene propanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy, C7-C9 side chain alkyl ester, manufactured by BASF Co., Ltd., Irganox 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl) ) -o-cresol, BASF Co., Ltd.), Irganox 3125 (Irganox 3125, BASF Co., Ltd.), Irganox 565 (Irganox 565: 2,4-bis(n-octylthio)-6- (4-hydroxy 3',5'-di-tert-butylanilino)-1,3,5-triazine, manufactured by BASF Co., Ltd., Adekastab AO-80 (Adekastab AO-80: 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxa Spiro (5,5) undecane, manufactured by ADEKA Co., Ltd.), Smirizer BHT (S) umilizer BHT, Sumitomo Chemical Co., Ltd.), Sumilizer GA-80 (Sumitomo Chemical Co., Ltd.), Sumilizer GS (Sumitomo Chemical Co., Ltd.), Cyanox 1790 (Cyanox 1790, manufactured by Cytech Co., Ltd.) and Vitamin E (manufactured by Eisai Co., Ltd.); and the like.

As said phosphorus antioxidant, Irgafos 168 (Irgafos 168: tris (2,4-di-tert-butylphenyl) phosphite, manufactured by BASF Co., Ltd.), Irgafos 12 (Irgafos 12: tris [2-[ [2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphin-6-yl]oxy]ethyl]amine, manufactured by BASF Co., Ltd.), Irgafos 38 (Irgafos 38: bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl ester phosphorous acid, manufactured by BASF Co., Ltd.), Adecastab 329K (manufactured by ADEKA Co., Ltd.) , Adekastab PEP36 (manufactured by ADEKA Co., Ltd.), Adekastab PEP-8 (manufactured by ADEKA Co., Ltd.), Sandstab P-EPQ (manufactured by Clariant Corporation), Weston 618 (Weston 618, manufactured by GE Corporation), Weston 619G (Weston 619G, manufactured by GE), Ultranox 626 (Ultranox 626, manufactured by GE) and Sumilizer GP (Sumilizer GP: 6-[3-(3-tert-butyl-4-hydroxy-5- methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenz[d,f][1.3.2]dioxaphosphepine) (manufactured by Sumitomo Chemical Co., Ltd.); and the like.

Examples of the sulfur-based antioxidant include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl or distearyl, and polyols such as tetrakis[methylene(3-dodecylthio)propionate]methane. β-alkyl mercaptopropionic acid ester compounds and the like are exemplified.

<Other ingredients>

The colored curable resin composition of the present invention may contain additives known in the art, such as fillers, other high molecular compounds, adhesion accelerators, light stabilizers, and chain transfer agents, if necessary.

<Method for producing colored curable resin composition>

The colored curable resin composition of the present invention is a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E), a leveling agent (F) used as necessary, and polymerization It can be prepared by mixing the initiator (D1), antioxidant (H) and other components.

The pigment in the case of containing the pigment (Ab) is preferably mixed with 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, you may mix|blend a part or all of the said pigment dispersant and resin (B) as needed. The target colored curable resin composition can be prepared by mixing the remaining components with the pigment dispersion obtained in this way so as to have a predetermined concentration.

Regarding the colorant (A), it is preferable to prepare a solution by dissolving the dye in part or all of the solvent (E) in advance. It is preferable to filter the solution through a filter having a pore diameter of about 0.01 to 1 µm.

It is preferable to filter the colored curable resin composition after mixing with a filter having a pore diameter of about 0.01 to 10 µm.

<Method for producing color filter>

A colored pattern can be produced from the colored curable resin composition of the present invention. A photolithography method, an inkjet method, a printing method, etc. are mentioned as a manufacturing method of the said coloring pattern, 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, exposing the colored composition layer through a photomask and developing it. In the photolithography method, by not using a photomask at the time of exposure and/or not developing, a colored coating film that is a cured product of the coloring composition layer can be formed. The colored pattern or colored coating film thus formed is the color filter of the present invention.

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

As the substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass having a surface coated with silica, a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, aluminum on the substrate , silver, a silver/copper/palladium alloy thin film or the like is used. Other color filter layers, resin layers, transistors, circuits and the like may be formed on these substrates. Formation of each color pixel by the photolithography method can be performed under known or common equipment and conditions. For example, it is producible as follows.

First, a colored curable resin composition is applied onto a substrate, dried by heat drying (prebaking) and/or reduced pressure drying to remove volatile components such as a solvent, followed by drying to obtain a smooth colored composition layer.

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

As temperature in the case of heat-drying, 30-120 degreeC is preferable and 50-110 degreeC is more preferable. Moreover, as heating time, it is preferable that it is 10 second - 60 minutes, and it is more preferable that it is 30 second - 30 minutes.

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

The film thickness of the coloring composition layer is not specifically limited, What is necessary is just to select suitably according to the film thickness of the color filter made into the objective.

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

As a light source used for exposure, a light source generating light with a wavelength of 250 to 450 nm is preferable. For example, light less than 350 nm is cut using a filter that cuts the wavelength range, or light around 436 nm, 408 nm, and 365 nm is cut using a band pass filter that extracts these wavelength ranges. and can be selectively extracted. Specifically, 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 the entire exposure surface with parallel light rays and perform accurate alignment of 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 in contact with a developing solution. By developing, the unexposed part of the coloring composition layer is dissolved in the developing solution and removed. As the developing solution, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of the alkaline compound in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. In addition, the developing solution may contain a surfactant. Any of a paddle method, dipping method, spray method, etc. may be sufficient as the developing method. Further, the substrate may be tilted at an arbitrary angle during development. It is preferable to wash with water after image development.

Moreover, it is preferable to post-bake the obtained coloring pattern. The post-baking temperature is preferably 150 to 250°C and more preferably 160 to 235°C. As post-baking time, 1 to 120 minutes are preferable, and 10 to 60 minutes are more preferable.

A high-contrast color filter can be manufactured with the colored curable resin composition of the present invention. The color filter is useful as a color filter used in display devices (liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

(Example)

Hereinafter, the colored curable resin composition of the present invention will be described in more detail by way of Examples. Unless otherwise specified, "%" and "part" in examples are mass % and mass part.

[Synthesis Example 1: Synthesis of triarylmethane colorant (A-I-18)]

The following reaction was performed under nitrogen atmosphere. After adding 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N,N-dimethylformamide to a flask equipped with a cooling tube and a stirring device, the mixed solution was ice-cooled. After adding 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) little by little over 30 minutes under ice-cooling, the mixture was stirred for 1 hour while heating to room temperature. 10.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added little by little to the reaction solution, and the mixture was stirred at room temperature for 24 hours. After adding the reaction liquid little by little to 200 parts of ice water, it was allowed to stand at room temperature for 15 hours, and when water was removed by decantation, a viscous solid was obtained as a residue. After adding 60 parts of methanol to this viscous solid, it stirred at room temperature for 15 hours. After separating the precipitated solid by filtration, it was purified by column chromatography. The purified pale yellow solid was dried at 60°C under reduced pressure to obtain 9.8 parts of a compound represented by formula (C-I-18).

The following reaction was performed under nitrogen atmosphere. After adding 8.2 parts of the compound represented by formula (B-I-7), 10 parts of the compound represented by formula (C-I-18), and 20 parts of toluene to a flask equipped with a cooling tube and a stirring device, phosphorus oxychloride 12.2 parts were added, and it stirred at 95-100 degreeC for 3 hours. Then, after cooling the reaction mixture to room temperature, it was diluted with 170 parts of isopropanol. Next, after putting the diluted reaction solution into 300 parts of saturated brine, 100 parts of toluene was added and the mixture was stirred for 30 minutes. Stirring was then stopped and left still for 30 minutes to separate an organic layer and an aqueous layer. After the aqueous layer was discarded by separation operation, the organic layer was washed with 300 parts of saturated brine. After adding an appropriate amount of sagebrush (芒硝) to the organic layer and stirring for 30 minutes, it was filtered to obtain a dried organic layer. The obtained organic layer was solvent-distilled with an evaporator to obtain a bluish-purple solid. Furthermore, the blue-purple solid was dried at 60°C under reduced pressure to obtain 18.4 parts of a compound represented by the formula (A-II-18).

The following reaction was performed under nitrogen atmosphere. After adding 8 parts of the compound represented by Formula (A-II-18) and 396 parts of methanol to a flask equipped with a cooling tube and a stirring device, it was stirred at room temperature for 30 minutes to prepare a blue solution. Subsequently, after adding 396 parts of water to the blue solution, it was further stirred at room temperature for 30 minutes to obtain a reaction solution.

In a beaker, 53 parts of water was charged, and 11.8 parts of Keggin-type phosphotungstic acid (manufactured by Aldrich) and 53 parts of methanol were added to the water, and mixed at room temperature to prepare a tungstophosphoric acid solution.

The obtained tungstic acid solution was added dropwise over 1 hour into the previously prepared reaction solution. Furthermore, after stirring at room temperature for 30 minutes, it filtered to obtain a blue solid. After the obtained blue solid was added in 200 parts of methanol and dispersed for 1 hour, the operation of filtering was repeated twice. After throwing in the blue solid obtained by the said operation in 200 parts of water, disperse|dispersing for 1 hour, operation of filtering was repeated twice. The blue solid obtained by the said operation was dried at 60 degreeC under reduced pressure, and 17.1 parts of triarylmethane coloring agents (A-I-18) represented by Formula (A-I-18) were obtained.

[Synthesis Example 2: Synthesis of xanthene dye (1-38)]

20 parts of the compound represented by Formula (1x) and 200 parts of N-propyl-2,6-dimethylaniline (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light-shielding conditions, and the resulting solution was stirred at 110°C for 6 hours. After cooling the obtained reaction liquid to room temperature, it was added to a liquid mixture of 800 parts of water and 50 parts of 35% by weight hydrochloric acid and stirred at room temperature for 1 hour, and crystals were precipitated. The precipitated crystal was obtained as a residue of suction filtration and then dried to obtain a xanthene dye (1-38) represented by the formula (1-38).

[Synthesis Example 3: Synthesis of Resin (B1)]

An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, dropping funnel and stirrer to create a nitrogen atmosphere, 305 parts of ethyl lactate was added, and the flask was heated to 70°C and kept warm while stirring. Then, 46 parts of acrylic acid and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate (the compound represented by formula (I-1) and the compound represented by formula (II-1) are mixed in a molar ratio of 50: Mixed at 50.) 240 parts and 185 parts of ethyl lactate were dissolved to prepare a solution, and the dissolved solution was added dropwise into a flask kept at 70°C over 4 hours using a dropping funnel.

On the other hand, a solution in which 30 parts of polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts of ethyl lactate was added dropwise into the flask over 4 hours using another dropping funnel. After dripping of the polymerization initiator solution was completed, the temperature was maintained at 70°C for 4 hours, and then cooled to room temperature. The weight average molecular weight (Mw) was 9.1 × 10 ³ , the degree of dispersion was 2.1, solid content was 26% by mass, solid content. A resin (B1) solution having an acid value of 120 mg-KOH/g was obtained. Resin (B1) has structural units shown below.

[Synthesis Example 4: Synthesis of Resin (B2)]

An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, dropping funnel and stirrer to replace the flask with a nitrogen atmosphere, and 371 parts of propylene glycol monomethyl ether acetate was added and heated to 85°C while stirring. Then, 54 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate (the compound represented by formula (I-1) and the compound represented by formula (II-1) are mixed in a molar ratio of 50: Mixed at 50.) A mixed solution of 225 parts, vinyltoluene (isomer mixture) 81 parts, and propylene glycol monomethyl ether acetate 80 parts was added dropwise over 4 hours.

On the other hand, a mixed solution in which 30 parts of 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 160 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropping, the temperature was maintained at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B2)) having a B-type viscosity (23°C) of 246 mPas, a solid content of 37.5% by mass, and a solution acid value of 43 mg-KOH/g. . Resin (B2) had a weight average molecular weight (Mw) of 1.1×10 ⁴ and a degree of dispersion of 2.01. Resin (B2) has the following structural units.

Measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the resins obtained in Synthesis Examples 3 and 4 were performed under the following conditions using the GPC method.

Device; K2479 (manufactured by Shimadzu Corporation)

column; SHIMADZU Shim-pack GPC-80M

column temperature; 40℃

menstruum; Tetrahydrofuran (THF)

flow rate; 1.0mL/min

detector; RI

calibration standards; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

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

[Preparation Example 1: Preparation of Dispersion (1)]

10 parts of the triarylmethane colorant (A-I-18) obtained in Synthesis Example 1, 2 parts of a dispersant (BYK (registered trademark)-LPN6919 (manufactured by Big Chemie Japan)), and the resin (B2 obtained in Synthesis Example 4) ) (in terms of solid content) was mixed with 4 parts of propylene glycol monomethyl ether acetate and 84 parts of propylene glycol monomethyl ether acetate, and the triarylmethane colorant (A-I-18) was sufficiently dispersed using a bead mill to obtain a dispersion (1).

[Preparation Example 2: Preparation of Dispersion (2)]

12 parts of pigment (C.I. Pigment Blue 15:6), 2 parts of acrylic pigment dispersant, and 80.5 parts of propylene glycol monomethyl ether acetate were mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a dispersion (2). .

[Examples 1 to 8, Comparative Examples 1 to 3]

(Preparation of colored curable resin composition)

Dispersion (1) (contains 10% by mass of triarylmethane colorant (A-I-18)),

· Xanthene dye (1-38),

Anthraquinone dye (C.I. Solvent Blue 45; Savinyl Blue RS; manufactured by Clariant);

Dispersion (2),

· (B) Resin: Resin (B1),

- (C) polymeric compound: dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nihon Kayaku Co., Ltd.),

(D) Polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure® OXE 01; manufactured by BASF Co., Ltd.)

(F) Leveling agent: polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.),

· (E) solvent: ethyl lactate (EL),

- (E) Solvent: Propylene glycol monomethyl ether acetate (PGMEA) was mixed by the number shown in Table 3, and colored curable resin composition was obtained.

<Production of colored patterns>

After applying the colored curable resin composition on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Co.) by spin coating, it was prebaked at 100°C for 3 minutes to obtain a colored composition layer. After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) with a distance of 100 μm between the substrate on which the colored composition layer is formed and the quartz glass photo mask, under an air atmosphere of 150 mJ / cm 2 Light was irradiated with an exposure amount (based on 365 nm). As a photomask, one formed with a 100 µm line-and-space pattern was used. The colored composition layer after light irradiation was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24° C. for 60 seconds, washed with water, and then post-baked at 230° C. for 30 minutes in an oven, A coloring pattern was obtained.

<Measurement of film thickness>

For the obtained colored pattern, the film thickness was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 4. In addition, Table 4 shows the content of each component converted so that the total amount of the coloring agent (A) is 100 with respect to the coloring agent (A) contained in the colored curable resin composition obtained by mixing in the number of copies shown in Table 3.

<Chromaticity Evaluation>

For the obtained color pattern, the spectroscopy is measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinates (x, y ) and tristimulus values (Y) were measured. The higher the value of Y, the higher the brightness. The results are shown in Table 4.

<Contrast evaluation>

A colored coating film was produced by performing the same operation as in the preparation of the colored pattern except for not using a photomask at the time of exposure. With respect to the obtained colored coating film, a contrast meter (CT-1; manufactured by Tsubosaka Electric Co., Ltd., color difference meter BM-5A; manufactured by Topcon Co., Ltd., light source; F-10, polarizing film; manufactured by Tsubosaka Electric Co., Ltd.) was used. , the contrast was measured with a blank value of 30000. If the contrast in the colored coating film is high, it can be said that the contrast is similarly high also in the colored pattern. The results are shown in Table 4.

According to the colored curable resin compositions of Examples 1 to 3 and Comparative Example 2, the chromaticity coordinates of y are 0.095, the chromaticity coordinates of x are 0.136 to 0.139, and colored patterns with close chromaticities were obtained. Moreover, in Examples 1-3, compared with Comparative Example 2, a coloring pattern with high brightness was obtained, and a colored coating film showing high contrast was obtained.

According to the colored curable resin compositions of Examples 4 to 8 and Comparative Examples 1 and 3, the chromaticity coordinates of y are 0.095 and the chromaticity coordinates of x are 0.150 to 0.153, and colored patterns with close chromaticities were obtained. Moreover, in Examples 4-8, compared with Comparative Examples 1 and 3, a colored pattern with high brightness was obtained, and a colored coating film showing high contrast was obtained.

From the above, it is understood that a high-contrast colored pattern can be produced from the colored curable resin composition of the present invention. The color filter obtained from the colored curable resin composition of the present invention has excellent display properties and is useful as a material for a liquid crystal display device.

Claims (5)

containing a colorant, a resin, a polymerizable compound and a polymerization initiator;
The colorant includes a triarylmethane colorant containing Compound (A-I), a xanthene dye, and an anthraquinone dye,
The colored curable resin composition in which the content rate of the said xanthene dye in the said coloring agent is 1 mass % or more and 13.5 mass % or less.

[In Formula (A-I), [Y ² ] ^m- is an m-valent anion, and [Y ² ] ^m- is an anion having at least one element selected from the group consisting of molybdenum and phosphorus and an oxygen atom. indicates
R ⁴¹ to R ⁴⁴ are, independently of each other, a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted, a group in which oxygen atoms are inserted between carbon atoms constituting an alkyl group having 2 to 20 carbon atoms, which may be substituted; An aryl group or an aralkyl group which may be substituted is shown. R ⁴¹ and R ⁴² may be bonded together to form a ring with the nitrogen atom to which they are bonded, or R ⁴³ and R ⁴⁴ may be bonded together with the nitrogen atom to which they are bonded to form a ring.
R ⁴⁵ to ^{R 52} are each independently a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms, or an oxygen atom inserted between carbon atoms constituting an alkyl group having 2 to 8 carbon atoms, group, or R ⁴⁶ and R ⁵⁰ may be bonded to each other to form -O-, -NH-, -S- or -SO ₂ -.
Y ¹ represents an optionally substituted aryl group or an optionally substituted heteroaryl group.
When the compound (A-I) contains a plurality of cations, the plurality of cations may have the same structure or different structures.
m represents any natural number.] According to claim 1,
The content of the anthraquinone dye is 0.5 to 50 parts by mass based on 100 parts by mass of the triarylmethane colorant, the colored curable resin composition. According to claim 2,
The content of the anthraquinone dye is 1.0 to 13.5 parts by mass with respect to 100 parts by mass of the triarylmethane colorant, the colored curable resin composition. A color filter formed from the colored curable resin composition according to any one of claims 1 to 3. A display device comprising the color filter according to claim 4 .