TWI770067B - Colored curable resin composition, color filter and displayer - Google Patents

Abstract

A colored curable resin composition comprises a colorant, a resin, a polymerizable compound and a polymerization initiator, wherein the colorant comprises a triarylmethane colorant, a xanthene dye, and an anthraquinone dye.

Description

Colored curable resin composition, color filter, and display device

The present invention relates to a colored curable resin composition.

Japanese Patent Application Laid-Open No. 2015-199912 discloses a coloring curable resin composition for forming color filters included in liquid crystal display devices, etc., solid-state imaging devices, etc., which contains a triarylmethane dye and a diarylmethane dye. A benzopyran dye is used as a coloring curable resin composition as a colorant.

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

[1] A colorable curable resin composition containing: a colorant, a resin, a polymerizable compound, and a polymerization initiator; the colorant containing: a triarylmethane colorant, a dibenzopyran dye, and an anthracene Quinone dyes.

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

[3] The colorable curable resin composition according to [2], wherein the content of the anthraquinone dye is 1.0 to 13.5 parts by mass relative to 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 comprising the color filter described in [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 colorable curable resin composition of the present invention preferably contains a solvent (E) and/or a leveling agent (F), and may also contain an antioxidant (H) and other components. The colorant (A) contains a triarylmethane colorant (Aa1), a dibenzopyran dye (Aa2), and an anthraquinone dye (Aa3). Since the colored curable resin composition of the present invention has the above-mentioned constitution, a high-contrast color filter can be produced.

<Colorant (A)>

The colorant (A) contains a triarylmethane colorant (Aa1), a dibenzopyran dye (Aa2), and an anthraquinone dye (Aa3). In addition, a dye (hereinafter sometimes referred to as "dye (Aa4)") different from the triarylmethane colorant (Aa1), the dibenzopyran dye (Aa2), and the anthraquinone dye (Aa3) may be contained.

(Triarylmethane Colorant (Aa1))

The triarylmethane colorant (Aa1) is a colorant including a compound having a triarylmethane skeleton in the molecule. Examples of the colorant include dyes and pigments, and may be laked pigments. The triarylmethane colorant (Aa1) is preferably a dye containing the compound represented by the formula (A-I) and the tautomer (hereinafter, these may be collectively referred to as "compound (A-I)").

When the compound (A-I) is used, the content of the compound (A-I) in the triarylmethane colorant (Aa1) is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 90% by mass or more. Among them, it is preferable to use only the compound (A-I) as the triarylmethane colorant (Aa1).

[In formula (AI), [Y ² ] ^m- represents an m-valent anion; R ⁴¹ to R ⁴⁴ independently represent a hydrogen atom, a substituted saturated hydrocarbon group having 1 to 20 carbon atoms, and each of which constitutes a carbon number of 2 A group in which an oxygen atom is inserted between the carbon atoms of the alkyl group to 20, an aryl group which may be substituted, or an aralkyl group which may be substituted; R ⁴¹ and R ⁴² may be bonded and with these bonded nitrogen atoms Form a ring together, R ⁴³ and R ⁴⁴ can bond and form a ring together with these bonded nitrogen atoms; R ⁴⁵ to R ⁵² independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a carbon number of 1 A saturated hydrocarbon group of to 8, or a group in which an oxygen atom is inserted between the carbon atoms constituting an alkyl group of 2 to 8 carbon atoms, or R ⁴⁶ and R ⁵⁰ are bonded to each other to form -O-, -NH-, -S -or -SO ₂ -; Y ¹ represents a substituted aryl group or a substituted heteroaryl group; when the compound represented by formula (AI) contains multiple cations, the multiple cations may have the same structure as each other or dissimilar structure; 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 can form a counter ion with the dye cation, and is preferably a boron-containing anion, an aluminum-containing anion, a fluorine-containing anion, a chloride anion, or the like. Halogen anions, and anions having at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and an oxygen atom.

Examples of boron-containing anions and aluminum-containing anions include anions represented by formula (4).

[W ¹ -MW ² ] ^Θ (4)

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

In the formula (4), compounds having two monovalent proton-donating substituents include compounds having two monovalent proton-donating substituents (eg, a hydroxyl group and a carboxyl group). For example, two Hydroxynaphthalene, optionally substituted 2,2'-biphenol, optionally substituted 3-hydroxy-2-naphthoic acid, optionally substituted 2-hydroxy-1-naphthoic acid, optionally substituted 1 -Hydroxy-2-naphthoic acid, optionally substituted dinaphthol, optionally substituted salicylic acid, optionally substituted benzoic acid, or optionally substituted mandelic acid.

The group formed by releasing a proton from the compound is a group formed by dissociating all protons from a plurality of proton-donating substituents in the compound, and means a group having O ^- or COO ^- .

The compound is preferably 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-naphthoic acid, optionally substituted 2-hydroxy-1-naphthoic acid, optionally substituted 1-hydroxy-2-naphthoic acid, optionally substituted dinaphthol, optionally substituted salicylic acid, Benzoic acid which may have a substituent or mandelic acid which may have a substituent.

In each of the aforementioned compounds, the substituents include saturated hydrocarbon groups (alkyl, cycloalkyl, etc.), halogen atoms, hydroxyl groups, amino groups, nitro groups, alkoxy groups, and the like.

The salicylic acid which may have a substituent includes salicylic acid, 3-methyl salicylic acid, 3-tert-butyl salicylic acid, 3-methoxysalicylic acid, 3-nitrosalicylic acid, and 4-trifluoromethane. Monoamine group of salicylic acid, 3,5-bis(tertiary butyl) salicylic acid, 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, etc. Salic acid; 3-hydroxysalicylic acid (2,3-dihydroxybenzoic acid), 4-hydroxysalicylic acid (2,4-dihydroxybenzoic acid), 5-hydroxysalicylic acid (2,5-dihydroxybenzoic acid) , Monohydroxysalicylic acid such as 6-hydroxysalicylic acid (2,6-dihydroxybenzoic acid); Monohalogen salicylic acid such as salicylic acid, 4-chlorosalicylic acid, 5-chlorosalicylic acid, 6-chlorosalicylic acid, 3-bromosalicylic acid, 4-bromosalicylic acid, 5-bromosalicylic acid, 6-bromosalicylic acid, etc. ; 3,5-dichlorosalicylic acid, 3,5-dibromosalicylic acid, 3,5-diiodosalicylic acid, etc., dihalosalicylic acid; 3,5,6-triclosalic acid, etc. Wait.

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

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

The anion represented by the formula (4) is preferably an anion represented by the following formula, and examples thereof include the anions (BC-1) to (BC-24) described in Table 1, and those represented by the formula (BC-24), respectively. -25), formula (BC-26), formula (BC-27) and formula (BC-28) represented by anion (BC-25) to anion (BC-28) and the like.

[In the formula, 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]

The anion represented by the formula (4) is preferably an anion (BC-1), an anion (BC-2), an anion (BC-3), an anion (BC-25), an anion (BC-26), an anion (BC-26), an anion (BC-2). BC-27), particularly preferably anion (BC-1), anion (BC-2), anion (BC-25), more preferably anion (BC-1), anion (BC-2). The compound represented by formula (A-I) having any of these anions tends to have excellent solubility in organic solvents.

As a fluorine-containing anion, the group represented by Formula (6), (7), (8), (9) is mentioned, for example.

[In formula (6), W ³ and W ⁴ independently represent a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms, or W ³ and W ⁴ are integrated to represent a fluorocarbon having 1 to 4 carbon atoms two bases]

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

^Θ O ₃ SY ^a -SO ₃ ^Θ (8)

[In formula (8), Y ^a represents a fluoroalkanediyl group having 1 to 4 carbon atoms]

Y ^b -SO ₃ ^Θ (9)

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

In formulas (6), (7) and (9), the fluoroalkyl group having 1 to 4 carbon atoms is preferably a perfluoroalkyl group. Examples of the perfluoroalkyl group include -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 formulas (6) and (8), the fluoroalkanediyl having 1 to 4 carbon atoms includes perfluoroalkanediyl, and preferably -CF ₂ -, -CF ₂ CF ₂ -, and -CF ₂ CF are exemplified. ₂ CF ₂ -, -C(CF ₃ ) ₂ -, -CF ₂ CF ₂ CF ₂ CF ₂ - and the like.

The anion represented by the formula (6) (hereinafter sometimes referred to as "anion (6)") includes the anions represented by the formula (6-1) to the formula (6-6) (hereinafter sometimes referred to as the formula (6-6). is "anion (6-1) to anion (6-6)").

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

The anion represented by the formula (8) (hereinafter sometimes referred to as "anion (8)") includes the anions represented by the formula (8-1) to the formula (8-4) (hereinafter sometimes referred to as the formula (8-4). are "anion (8-1)" to "anion (8-4)").

^Θ O ₃ S-CF ₂ -SO ₃ ^Θ (8-1) ^Θ O ₃ S-CF ₂ CF ₂ CF ₂ -SO ₃ ^Θ (8-3)

^Θ O ₃ S-CF ₂ CF ₂ -SO ₃ ^Θ (8-2) ^Θ O ₃ S-CF ₂ CF ₂ CF ₂ CF ₂ -SO ₃ ^Θ (8-4)

The anion represented by formula (9) (hereinafter sometimes referred to as "anion (9)") includes anions (hereinafter sometimes referred to as formula (9-1) to formula (9-4), respectively). are "anion (9-1)" to "anion (9-4)").

F ₃ C-SO ₃ ^Θ (9-1) F ₃ CF ₂ CF ₂ C-SO ₃ ^Θ (9-3)

F ₃ CF ₂ C-SO ₃ ^Θ (9-2) F ₃ CF ₂ CF ₂ CF ₂ C-SO ₃ ^Θ (9-4)

[Y ² ] ^m- is preferably a fluorine-containing anion, a polyacid anion, particularly preferably an anion represented by the 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- , more preferably an anion represented by formula (6-1) to formula (6-5), [PW ₁₂ O ₄₀ ] ^3- , and [P ₂ W ₁₈ O ₆₂ ] ^6- , particularly preferably an anion represented by the formula (6-2) and [PW ₁₂ O ₄₀ ] ^3- .

m represents an arbitrary natural number, which is equal to the negative charge possessed by the anion [Y ² ] ^m- . The m on the cation side is determined so that the charges of the anion [Y ² ] ^m- and the cation become equal. m is preferably a natural number from 1 to 10.

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

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

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

The hydrogen atom of the saturated hydrocarbon group of R ⁴¹ to R ⁴⁴ may be substituted by a substituent. Examples of the substituent include substituted or unsubstituted amine groups and halogen atoms. Examples of the substituted amino group include dialkylamine groups such as a dimethylamino group, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of saturated hydrocarbon groups in which hydrogen atoms are substituted with substituted or unsubstituted amine groups or halogen atoms include groups represented by the following formulae. In the following formula, * represents a bond with a nitrogen atom.

Among the groups represented by R ⁴¹ to R ⁴⁴ , groups in which an oxygen atom is inserted between methylene groups (carbon atoms) constituting an alkyl group having 2 to 20 carbon atoms include, for example, groups represented by the following formulae . In the following formula, * represents a bond with a nitrogen atom. Among them, the group in which an oxygen atom is inserted between the methylene groups constituting the alkyl group is preferably a group having 2 to 10 carbon atoms, and particularly preferably a group having 2 to 6 carbon atoms. The alkyl group into which an oxygen atom is inserted is preferably a straight-chain alkyl group. Further, the number of carbon atoms between oxygen atoms is preferably 1 to 4, and particularly preferably 2 to 3.

In R ⁴¹ to R ⁴⁴ , the carbon number of the aryl group is preferably 6 to 20, particularly preferably 6 to 10, and the carbon number of the aralkyl group is preferably 7 to 20, particularly preferably 7 to 10.

The aryl group of R ⁴¹ to R ⁴⁴ includes a phenyl group, a naphthyl group, a tolyl group and the like.

Examples of the aryl group in the aralkyl group of R ⁴¹ to R ⁴⁴ include a phenyl group, a naphthyl group, and the like, and the aralkyl group includes a group in which a bond of these aryl groups and an alkanediyl group are bonded. The carbon number of the aforementioned alkanediyl group is preferably 1 to 10, particularly preferably 1 to 5, and is preferably a linear alkanediyl group. Specific examples of the alkanediyl group include methylene group, ethylidene group, propylidene group, butanediyl group, pentanediyl group, and the like, and the aralkyl group includes benzyl group, phenethyl group, naphthylmethyl group, and naphthylethyl group. Base et al.

Among the groups represented by R ⁴¹ to R ⁴⁴ , in the aryl group and the aralkyl group, the substituents include halogen atoms such as fluorine atom, chlorine atom, iodine atom, etc.; carbon number such as methoxy group, ethoxy group, etc. Alkoxy groups of 1 to 6; hydroxyl; alkylsulfonyl groups of 1 to 6 carbon atoms such as methylsulfonyl; alkoxycarbonyl groups of 2 to 6 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, and the like.

Specific examples of the aryl group which may be substituted include groups represented by the following formulae. In the following formula, * represents a bond with a nitrogen atom.

Specific examples of the aralkyl group which may be substituted include a group in which an alkylene group such as a methylene group and an ethylidene group is bonded to the bonding bond of the aforementioned aryl group.

R ⁴¹ and R ⁴² may bond and form a ring together with these bonded nitrogen atoms, and R ⁴³ and R ⁴⁴ may bond and form a ring with these bonded nitrogen atoms, and pyrrolidine can be exemplified (Pyrrolidine) and other 5-membered rings; Morpholine (Morpholine) ring, piperidine (Piperidine) ring, piperazine (Piperazine) ring and other 6-membered rings.

R ⁴¹ to R ⁴⁴ are preferably independently substituted saturated hydrocarbon groups having 1 to 20 carbon atoms, optionally substituted aryl groups, or optionally substituted aralkanes, from the viewpoint of ease of synthesis. The groups are 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 any of linear, branched and cyclic, preferably chain. The saturated hydrocarbon group represented by R ⁴⁵ to R ⁵² includes a group having 1 to 8 carbon atoms among the groups exemplified in the saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁴ .

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

R ⁴⁵ to R ⁵² are preferably independently a hydrogen atom, a halogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms, and are particularly preferably independently a hydrogen atom, methyl group, fluorine atom or chlorine atom.

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

Y ¹ represents an aryl group which may be substituted, or a heteroaryl group which may be substituted.

The aryl group may be either a single ring or a condensed ring, and examples thereof include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthranyl group, a phenanthryl group, a biphenyl group, and a bitriphenyl group. Aromatic hydrocarbon groups with 6 to 20 carbon atoms.

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

The monocyclic aromatic heterocyclic ring includes five members having a nitrogen atom such as a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, and a thiazole ring. Ring; Furan (Furan) ring, Thiophene (Thiophene) ring and other 5-membered rings with oxygen atom or sulfur atom; Pyridine (Pyridine) ring, pyrimidine (Pyrimidine) ring, pyridazine (Pyridazine) ring, Pyrazine A 6-membered ring having a nitrogen atom, etc., is included in the ring. The aromatic heterocycle of the condensed ring includes a condensed ring having a nitrogen atom such as an indole ring, a benzimidazole ring, a benzothiazole ring, and a quinoline ring; and an oxygen atom such as benzofuran. atom or sulfur atom etc. The heteroaryl group which may be substituted is particularly preferably a group represented by the formula (Ab2-x1).

[Ring T ² represents an aromatic heterocycle; R ⁵³ and R ⁵⁴ independently represent a substituted saturated hydrocarbon group with 1 to 20 carbon atoms, and oxygen is inserted between the carbon atoms constituting the alkyl group with 2 to 20 carbon atoms Atomic group, aryl group that can be substituted, aralkyl group that can be substituted, or hydrogen atom; R ⁵⁵ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aryl group that can be substituted; k1 represents 0 or 1; * indicates a bond with a carbocation]

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

Details of R ⁵³ to R ⁵⁵ will be described later.

The compound (A-I) is particularly preferably a compound represented by the formula (A-II).

[In formula (A-II), [Y ² ] ^m- , R ⁴¹ to R ⁵² and m are the same as described above; R ⁵³ and R ⁵⁴ independently represent a hydrogen atom, a substituted carbon number of 1 to 20 A saturated hydrocarbon group, a group in which an oxygen atom is inserted between carbon atoms constituting an alkyl group having 2 to 20 carbon atoms, an aryl group that may be substituted, or an aralkyl group that may be substituted; R ⁵⁵ represents a hydrogen atom, a carbon number of 1 to 20 A saturated hydrocarbon group of 20, or an aryl group that can be substituted; 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 represented by formula (A-II) When the compound represented contains multiple cations, the multiple cations may have the same structure or different structures]

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

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁵⁵ include the same groups as those exemplified in the saturated hydrocarbon group of R ⁴¹ to R ⁴⁴ . Among them, an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 8 carbon atoms is particularly preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is particularly preferred.

The group represented by R ⁵⁵ in which an oxygen atom is inserted between carbon atoms constituting the above-mentioned alkyl group includes the same groups as those exemplified in R ⁴¹ to R ⁴⁴ . The alkyl group into which an oxygen atom is inserted is preferably a straight-chain alkyl group. Further, the number of carbon atoms between oxygen atoms is preferably 1 to 4, and particularly preferably 2 to 3.

In R ⁵⁵ , the carbon number of the aryl group is preferably from 6 to 20, particularly preferably from 6 to 10. Examples of the aryl group include the same groups as the aryl groups exemplified in R ⁴¹ to R ⁴⁴ , and preferably a phenyl group.

In R ⁵⁵ , the substituents possessed by the aryl group include halogen atoms such as fluorine atoms, chlorine atoms, and iodine atoms; alkoxy groups having 1 to 6 carbon atoms such as methoxy groups and ethoxy groups; hydroxyl groups; amines Sulfonyl; alkylsulfonyl having 1 to 6 carbons such as methylsulfonyl; alkoxycarbonyl having 2 to 6 carbons such as methoxycarbonyl, ethoxycarbonyl and the like.

R ⁵⁵ is preferably a saturated hydrocarbon group having 1 to 10 carbon atoms or an aryl group that may be substituted, particularly preferably an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms, or a halogen atom, The aryl group substituted with an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, or a methylsulfonyl group is more preferably 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, particularly preferably a methyl group.

X represents an oxygen atom, -NR ⁵⁷ - or a sulfur atom. Examples of the cyclic structure containing X include groups represented by the following formulae. In the formula, R ⁵³ to R ⁵⁵ are respectively synonymous with the above, and * represents a bond with a carbocation. Among them, X is preferably an oxygen atom or a sulfur atom, and particularly preferably a sulfur atom.

The cations of formula (A-I) are cations represented by formula (A-I-1), and cations 1 to 27 having substituents shown in Table 2 are exemplified.

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

The cations in the formula (A-I) are preferably cation 1 to cation 6, cation 11 and cation 12, and particularly preferably cation 1, cation 2 and cation 12.

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

(Dibenzopyran dye (Aa2))

Dibenzopyran dye (Aa2) is a dye containing a compound having a dibenzopyran skeleton in the molecule. Dibenzopyran dyes (Aa2) include C.I. Acid Red 51 (hereinafter, the description of C.I. Acid Red is omitted, and only the number is described. The same applies to others), 52, 87, 92, 94, 289, 388; C.I. Acid Violet 9, 30, 102; C.I. Basic Red 1 (Rose Red 6G), 2, 3, 4, 8; C.I. Basic Red 10 (Rose Red B), 11; C.I. Basic Violet 10, 11, 25; C.I. Solvent Red 218; C.I. Mordant Red Mordant Red 27; C.I. Reactive Red 36 (Rose Bengal B), Sulfo Rose Bengal G, Dibenzopyran dyes described in Japanese Patent Laid-Open No. 2010-32999 and Japanese Patent No. 4492760 Dibenzopyran dyes and the like described in the gazette. Among them, dibenzopyran dyes dissolved in organic solvents are preferred.

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

[In formula (1a), R ¹ to R ⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group with 6 to 10 carbon atoms that may have a substituent , the hydrogen atom contained in the saturated hydrocarbon group may be replaced by an aromatic hydrocarbon group with a carbon number of 6 to 10 or a halogen atom, and the hydrogen atom contained in the aromatic hydrocarbon group may be replaced by an alkoxy group with a carbon number of 1 to 3 Substitution, the -CH ₂ - contained in the aforementioned saturated hydrocarbon group can be replaced by -O-, -CO- or -NR ¹¹ -; R ¹ and R ² can be integrated to form a ring containing nitrogen atoms, R ³ and R ⁴ Can be integrated to form a ring containing nitrogen atoms; R ⁵ represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ ; R ⁶ and R ⁷ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m represents an integer of 0 to 5; m is 2 or more When the integer of R ⁵ can 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 with 1 to 20 carbon atoms, and the hydrogen contained in the saturated hydrocarbon group Atom, which may be substituted by a halogen atom; Z ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ ; R ⁹ and R ¹⁰ independently represent a hydrogen atom or a substituent with 1 to 20 carbon atoms. Monovalent saturated hydrocarbon group, the -CH ₂ - contained in the saturated hydrocarbon group can be replaced by -O-, -CO-, -NH- or -NR ⁸ -; R ⁹ and R ¹⁰ can be bonded to each other to form nitrogen-containing A 3- to 10-membered heterocyclic ring of atoms; 4 R ¹¹ in ⁺ N(R ¹¹ ) ₄ independently represent a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms, or a monovalent saturated hydrocarbon group with 7 to 20 carbon atoms. 10 aralkyl]

A phenyl group, a tolyl group, a xylyl group, a mesityl group, a propylphenyl group, a butylphenyl group, etc. are mentioned as a monovalent aromatic hydrocarbon group which shows R< ¹ >-R< ⁴ >.

The substituent which the aromatic hydrocarbon group may have includes 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, the substituents are preferably -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ , particularly preferably -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ . In this case, -SO ₃ ^- Z ⁺ is preferably -SO ₃ ^-+ N(R ¹¹ ) ₄ . When R ¹ to R ⁴ are such groups, from the colored curable resin composition of the present invention containing the compound (1a), a color filter with less generation of impurities and excellent heat resistance can be formed.

The ring formed by the integration of R ¹ and R ² and the ring formed by the integration of R ³ and R ⁴ include, for example, those shown below.

The monovalent saturated hydrocarbon group representing R ⁸ to R ¹¹ includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, Linear alkyl groups such as hexadecyl, eicosyl, etc.; branched chain alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl, etc.; cyclopropyl , cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl and other alicyclic saturated hydrocarbon groups with 3 to 20 carbon atoms.

-OR ⁸ includes methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, and eicosane Oxygen, etc.

-CO ₂ R ⁸ includes methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tertiary butoxycarbonyl, hexyloxycarbonyl, eicosyloxycarbonyl, and the like.

As SR ⁸ , methyl thiosulfanyl, ethyl sulfhydryl, butyl sulfhydryl, hexyl sulfhydryl, decyl sulfhydryl, eicosyl sulfhydryl, and the like are exemplified.

-SO ₂ R ⁸ includes methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl, eicosylsulfonyl, and the like.

-SO ₃ R ⁸ , methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tertiary butoxysulfonyl, hexyloxysulfonyl, and eicosyloxy Sulfonyl, etc.

-SO ₂ NR ⁹ R ¹⁰ , sulfasulfonyl; Sulfonyl, N-butylaminesulfonyl, N-isobutylaminesulfonyl, N-second-butylaminesulfonyl, N-tertiary-butylaminesulfonyl, N-amylaminesulfonyl Acyl, N-(1-ethylpropyl) sulfamoyl, N-(1,1-dimethylpropyl) sulfamoyl, N-(1,2-dimethylpropyl) amine Sulfonyl, N-(2,2-dimethylpropyl) sulfamoyl, N-(1-methylbutyl) sulfamoyl, N-(2-methylbutyl) sulfamoyl base, N-(3-methylbutyl) sulfamoyl, N-cyclopentyl sulfamoyl, N-hexyl sulfamoyl, N-(1,3-dimethylbutyl) sulfamoyl Sulfonyl, N-(3,3-dimethylbutyl)sulfamoyl, N-heptylsulfamoyl, N-(1-methylhexyl)sulfamoyl, N-(1,4 -Dimethylpentyl) sulfamoyl, N-octyl sulfamoyl, N-(2-ethylhexyl) sulfamoyl, N-(1,5-dimethyl)hexyl sulfamoyl N-1-substituted sulfamoyl group, N-(1,1,2,2-tetramethylbutyl) sulfamoyl group, etc.; N,N-dimethylsulfamoyl group, N,N- Ethylmethylaminosulfonyl, N,N-diethylaminosulfonyl, N,N-propylmethylaminosulfonyl, N,N-isopropylmethylaminosulfonyl, N, N-tertiary butylmethylsulfamoyl, N,N-butylethylsulfamoyl, N,N-bis(1-methylpropyl)sulfamoyl, N,N-heptylmethyl N,N-2 substituted sulfamoyl groups such as sulfamoyl groups, etc.

The substituent in the monovalent saturated hydrocarbon group representing R ⁹ or R ¹⁰ includes a hydroxyl group and a halogen atom.

R ⁵ is preferably -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H or -SO ₂ NHR ⁹ , particularly preferably - SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H or -SO ₂ NHR ⁹ .

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

The alkyl group having 1 to 6 carbon atoms representing R ⁶ and R ⁷ may be a straight chain or a branched chain, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, and hexyl.

The aralkyl group representing R ¹¹ includes a benzyl group, a phenylethyl group, a phenylbutyl group, and the like.

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

In the aforementioned ⁺ N(R ¹¹ ) ₄ , among the four R ¹¹ , at least two of them are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total carbon number of the four R ^11s is preferably from 20 to 80, particularly preferably from 20 to 60. When ⁺ N(R ¹¹ ) ₄ is present in the compound (1a), if R ¹¹ is such a group, the color curable resin composition of the present invention containing the compound (1a) can form a color with few impurities filter.

Preferable examples of the compound (1a) include the compound represented by the formula (2a) and the tautomer (hereinafter, these may be collectively referred to as "compound (2a)"). When the compound (2a) is used, the content of the compound (2a) in the dibenzopyran dye (A2) is preferably 50% by mass or more, more preferably 70% by mass or more, and 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 substituent which may have a monovalent substituent of 6 to 10 carbon atoms; R ¹¹ and R ²² can be integrated to form a ring containing nitrogen atoms, R ²³ and R ²⁴ can be integrated to form a ring containing nitrogen atoms; R ²⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ or - SO ₂ NHR ²⁶ ; m1 represents an integer from 0 to 5; when m1 is an integer of 2 or more, 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 the carbon number Monovalent saturated hydrocarbon group of 1 to 20; Z1 ⁺ represents ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ ; 4 R ²⁷ in ⁺ N(R ²⁷ ) ₄ independently represent carbon number 1 Monovalent saturated hydrocarbon group or benzyl group to 20]

The monovalent aromatic hydrocarbon group representing R ²¹ to R ²⁴ can be the same as the aromatic hydrocarbon group exemplified in the aforementioned R ¹ to R ⁴ ; the hydrogen atom contained in the aromatic hydrocarbon group can be represented by -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ .

The combination of R ²¹ to R ²⁴ is preferably that 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 ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ . A more preferable combination is that R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups with 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon groups are -SO ₃ ^- Z1 ⁺ or - SO ₂ NHR ²⁶ superseded. When R ²¹ to R ²⁴ are such groups, a color filter excellent in heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (2a).

The ring containing a nitrogen atom formed by the integration of R ²¹ and R ²² , and the ring containing a nitrogen atom formed by the integration of R ²³ and R ²⁴ , are the same as the ring formed by the integration of R ¹ and R ² . ring. Among them, an aliphatic heterocycle is preferred. Examples of the aliphatic heterocycle include those shown below.

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

When R ²¹ to R ²⁴ are -R ²⁶ , -R ²⁶ is preferably independently methyl or ethyl. R ²⁶ in -SO ₃ R ²⁶ and -SO ₂ NHR ²⁶ is preferably a branched chain alkyl group having 3 to 20 carbon atoms, particularly preferably a branched chain alkyl group having 6 to 12 carbon atoms, more preferably For 2-ethylhexyl. When R ²⁶ is such a group, a color filter with little generation of impurities 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 .

In the aforementioned ⁺ N(R ²⁷ ) ₄ , among the four R ²⁷ , at least two of them are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. Further, the total carbon number of the four R ^27s is preferably from 20 to 80, particularly preferably from 20 to 60. When ⁺ N(R ²⁷ ) ₄ is present in the compound (2a), the colored curable resin composition of the present invention containing the compound (2a) in which R ²⁷ is such a group can form a color filter with less generation of impurities. light sheet.

m1 is preferably 1 to 4, particularly preferably 1 or 2.

Preferable examples of the compound (1a) include the compound represented by the formula (3a) and the tautomer (hereinafter, these may be collectively referred to as "compound (3a)"). When the compound (3a) is used, the content of the compound (3a) in the dibenzopyran dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 90% by mass or more.

[In formula (3a), R ³¹ and R ³² each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group can be converted to an aromatic hydrocarbon group having 6 to 10 carbon atoms, Or halogen atom, the hydrogen atom contained in the aromatic hydrocarbon group can be substituted by an alkoxy group with 1 to 3 carbon atoms, the -CH ₂ - contained in the aforementioned saturated hydrocarbon group can be replaced by -O-, -CO- or -NR ¹¹ -replacement; R ³³ and R ³⁴ independently represent an alkyl group with 1 to 4 carbon atoms, an alkyl hydrogen thio group with 1 to 4 carbon atoms or an alkylsulfonyl group with 1 to 4 carbon atoms; R ³¹ and R ³³ may be integrated to form a ring containing a nitrogen atom, R ³² and R ³⁴ may be integrated to form a ring containing a nitrogen atom; p and q independently represent an integer from 0 to 5; p is 2 or more When , a plurality of R ³³ can be the same or different, and when q is 2 or more, a plurality of R ³⁴ can be the same or different; R ¹¹ represents the same meaning as above]

The monovalent saturated hydrocarbon group of R ³¹ and R ³² includes straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. ; Branched chain alkyl of isopropyl, isobutyl, isoamyl, neopentyl, 2-ethylhexyl, etc.; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, Alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms such as tricyclodecyl.

The aromatic hydrocarbon group which may have a substituent includes the same groups as the aromatic hydrocarbon group in R ¹ .

Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group.

Preferably, R ³¹ and R ³² are each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

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

^R33 and ^R34 have 1 to 4 alkyl hydrogen sulfhydryl groups, such as methyl sulfhydryl, ethyl sulfhydryl, propyl sulfhydryl, butyl sulfhydryl, and isopropyl sulfhydryl Base et al.

The alkylsulfonyl groups having 1 to 4 carbon atoms in R ³³ and R ³⁴ include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl and isopropylsulfonyl Base et al.

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

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

As the compound (1a), for example, compounds represented by formula (1-1) to formula (1-42) or formula (1-21′), respectively, can be exemplified. In the formula, R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms, more preferably 2-ethylhexyl. Compounds represented by formula (1-1) to formula (1-29) and formula (1-21') are equivalent to compound (2a), and are represented by formula (1-30) to formula (1-42) The compound corresponds to compound (3a).

Among these, the amide compound of C.I. Acid Red 289, the quaternary ammonium salt of C.I. Acid Red 289, the amide compound of C.I. Acid Violet 102, or the quaternary ammonium salt of C.I. Acid Violet 102 are preferable. Examples of the compound include compounds represented by formula (1-1) to formula (1-8), formula (1-11), and formula (1-12).

Compounds represented by formula (1-30) to formula (1-39) are preferred from the viewpoint of being excellent in solubility in organic solvents.

Dibenzopyran dye (Aa2), or commercially available dibenzopyran dye (such as "Chugai Aminol Fast Pink R-H/C" manufactured by Chugai Chemical Co., Ltd., "Chugai Aminol Fast Pink R-H/C" manufactured by Tianoka Chemical Industry Co., Ltd. Rhodamin 6G”). Commercially available dibenzopyran dyes can also be used as starting materials to synthesize with reference to Japanese Patent Laid-Open No. 2010-32999.

(Anthraquinone dye (Aa3))

The anthraquinone dye (Aa3) may be a generally known substance. Examples of the anthraquinone dye (Aa3) include: C.I. Solvent Yellow 117 (C.I. Solvent Yellow 117 is omitted below, and only the number is given), 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. Mordant Red 3, 11, C.I. Mordant Blue, etc. The anthraquinone dye is preferably dissolved in an organic solvent. Anthraquinone dyes, particularly preferably blue, violet or red.

The anthraquinone dye (Aa3) is preferably a compound represented by formula (1b) (hereinafter sometimes referred to as "compound (1b)").

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

[In formula (1b'), R ⁹³ represents 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 with 1 to 10 carbon atoms which may be substituted by a halogen atom, a hydroxyl group or an amine group, or a saturated hydrocarbon group with 3 to 10 carbon atoms which may be substituted with a halogen atom, a hydroxyl group or an amine group alicyclic hydrocarbon group; R ⁹⁵ represents a hydrogen atom, or a saturated hydrocarbon group with a carbon number of 1 to 10; r represents an integer from 0 to 5; when r is 2 or more, a plurality of R ⁹³ may be the same or different; X ⁹¹ represents single bond or alkanediyl having 1 to 6 carbon atoms]

When compound (1b) has _-SO3H and/or _-CO2H , these can form salts (eg, sodium or potassium salts).

The aliphatic hydrocarbon group represented by R ⁹¹ and R ⁹² includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isopropyl Alkyl groups having 1 to 10 carbon atoms such as butyl, tertiary butyl, tertiary butyl, isopentyl, neopentyl, 2-ethylhexyl and the like.

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

Alicyclic hydrocarbon groups represented by R ⁹¹ , R ⁹² and R ⁹⁴ include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl and the like, and have 3 to 10 carbon atoms cycloalkyl.

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

The alkyl group represented by R ⁹³ includes methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, tertiary butyl, tertiary butyl, and isopentyl. , Neopentyl, etc.

Saturated hydrocarbon groups represented by R ⁹⁴ and R ⁹⁵ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like having 1 to 10 carbon atoms the alkyl group.

-CO ₂ R ⁹⁴ includes methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tertiary butoxycarbonyl, hexyloxycarbonyl, and eicosoxycarbonyl.

-NHCOR ⁹⁴ , N-acetylamino, N-propionylamino, N-butyrylamino, N-isobutyrylamino, N-trimethylacetylamino, etc. are mentioned.

-SO ₃ R ⁹⁴ , such as methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tertiary butoxysulfonyl, hexyloxysulfonyl, and eicosoxy Sulfonyl etc.

-SO ₂ NR ⁹⁴ R ⁹⁵ , N-methyl sulfamoyl, N-ethyl sulfamoyl, N-propyl sulfamoyl, N-isopropyl sulfamoyl, N- Butyl sulfamoyl, N-isobutyl sulfamoyl, N-tertiary butyl sulfamoyl, N-tertiary butyl sulfamoyl, N-pentyl sulfamoyl, N- (1-ethylpropyl) sulfamoyl, N-(1,1-dimethylpropyl) sulfamoyl, N-(1,2-dimethylpropyl) sulfamoyl, N -(2,2-Dimethylpropyl) sulfamoyl, N-(1-methylbutyl) sulfamoyl, N-(2-methylbutyl) sulfamoyl, N-( 3-Methylbutyl) sulfamoyl, N-cyclopentyl sulfamoyl, N-cyclohexyl sulfamoyl, N-hexyl sulfamoyl, N-(1,3-dimethylbutyl) base) sulfamoyl, N-(3,3-dimethylbutyl) sulfamoyl, N-heptyl sulfamoyl, N-(1-methylhexyl) sulfamoyl, N- (1,4-Dimethylpentyl) sulfamoyl, N-octyl sulfamoyl, N-(2-ethylhexyl) sulfamoyl, N-(1,5-dimethyl) N-1 substituted sulfamoyl such as hexyl sulfamoyl, N-(1,1,2,2-tetramethylbutyl) sulfamoyl, N-(5-aminopentyl) sulfamoyl, etc. Sulfonyl; N,N-dimethylsulfamoyl, N,N-ethylmethylsulfamoyl, N,N-diethylsulfamoyl, N,N-propylmethylsulfanyl Sulfonyl, N,N-isopropylmethylsulfamoyl, N,N-tertiary butylmethylsulfamoyl, N,N-butylethylsulfamoyl, N,N-bis(1 -N,N-2-substituted sulfamoyl group such as -methylpropyl) sulfamoyl group, N,N-heptyl methyl sulfamoyl group, etc.

Alkanediyl representing X ⁹¹ includes methylene, ethylidene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane- 1,5-diyl, hexane-1,6-diyl, ethane-1,1-diyl, butane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, etc.

As the compound (1b), compounds represented by the formula (3-1) to the formula (3-11) can be exemplified.

Anthraquinone dye (Aa3), particularly preferably C.I. Solvent Blue 45. In the case of an anthraquinone dye such as this, a coating film or pattern with higher contrast can be formed, and a coating film or pattern with less generation of impurities and excellent light resistance can be formed.

(Dye (Aa4))

The dye (Aa4) is not particularly limited as long as it is different from the triarylmethane colorant (Aa1), the dibenzopyran dye (Aa2), and the anthraquinone dye (Aa3). The dye (Aa4) includes dyes such as oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, and sulfamide derivatives of acid dyes. Specifically, the dyes classified as dyes in the color index (published by The Society of Dyers and Colourists), that is, compounds classified as other than pigments, or generally known dyes described in dyeing notebooks (color dyeing companies) can be mentioned. According to chemical structures, azo dyes, cyanine dyes, phthalocyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, Squarylium dyes, acridine dyes, styryl dyes, coumarin dyes and nitro dyes, etc. Among these, organic solvent-soluble dyes are preferred.

Specific examples include: 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 Dye of C.I. Solvent Green 34, 35; C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31 , 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. acid dyes of C.I. Acid Green 58, 63, 65, 80, 104, 105, 106, 109, etc.; 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 , 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 C.I. Direct Dyes, etc.; 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. Mordant 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. Mordant 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. Mordant Green 1, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, etc. The C.I. Mordant Dyes, etc.

(Pigment (Ab))

The colored curable resin composition of the present invention may contain a pigment (Ab). The pigment (Ab) is not particularly limited, and generally 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).

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, 214 and other yellow pigments; C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51 ,55,59,61,64,65,71,73, etc , 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments; C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments; C.I. Pigment Violet 1, Purple pigments of 19, 23, 29, 32, 36, 38, etc.; green pigments of C.I. Pigment Green 7, 36, 58, etc.; brown pigments of C.I. Pigment Brown 23, 25, etc.; black pigments of C.I. Pigment Black 1, 7, etc. Wait.

Pigment (Ab), preferably blue pigment, especially phthalocyanine pigment and dioxazine pigment, more preferably at least one selected from the group consisting of C.I. Pigment Blue 15:6 and C.I. Pigment Violet 23 A sort of.

Pigment (Ab), if necessary, subject to rosin treatment, surface treatment using pigment derivatives introduced with acid groups or basic groups, etc., grafting treatment on the surface of the pigment according to polymer compounds, etc., according to the sulfuric acid micronization method Micronization treatment, washing treatment with organic solvent or water for removing impurities, removal treatment according to ion exchange method of ionic impurities, etc. The particle diameters of the pigments are preferably uniform, respectively.

Pigments can be dispersed in a pigment dispersant solution by containing a pigment dispersant to form a uniformly dispersed pigment dispersion liquid in a pigment dispersant solution. Pigments can be dispersed individually, or a plurality of them can be mixed and dispersed.

The aforementioned pigment dispersants include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigment dispersants. These pigment dispersants can be used alone or in combination of two or more. Pigment dispersants include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Fluorene (manufactured by Kyōeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), and EFKA (manufactured by BASF Co., Ltd.) , Ajisper (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (manufactured by BYK Chemie Co., Ltd.), etc.

When a pigment dispersant is used, the amount used is preferably 100 parts by mass or less, particularly preferably 5 parts by mass or more and 50 parts by mass or less, relative to 100 parts by mass of the pigment. When the amount of the pigment dispersant used is within the aforementioned range, there is a tendency to obtain a uniformly dispersed pigment dispersion.

In this specification, the compound as each component is exemplified, and unless otherwise specified, it can be used alone or in combination of plural kinds.

The content rate of the colorant (A) in the colorable curable resin is preferably 5 mass % or more and 70 mass % or less, more preferably 5 mass % or more and 60 mass % or less, more preferably 5 mass % or more and 50 mass % or less. When the content rate of the colorant (A) is within the aforementioned range, a desired spectral or color density can be obtained.

In this specification, "total amount of solid content" means the total amount of the component which subtracted the solvent (E) from the coloring curable resin composition of this invention. The total amount of solid components and the content of each component relative thereto can be measured by a generally known 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 light distribution, but the following ranges are preferred from the viewpoint of forming a high-contrast coating film or pattern.

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

The content of the dibenzopyran dye (Aa2) in the colorant (A) is preferably 0.1 mass % or more and 80 mass % or less, more preferably 0.5 mass % or more and 40 mass % or less, more preferably 1 mass % More than 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, and 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, and 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 relative to 100 parts by mass of the triarylmethane colorant (Aa1), more preferably 1.0 to 35 parts by mass, more preferably It is 1.0 to 13.5 parts by mass, particularly preferably 1.2 to 13.1 parts by mass. By making the content of the anthraquinone dye (Aa3) within the above range, a higher contrast coating film or pattern can be formed.

<Resin (B)>

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

As this resin (B), the following resins [K1] to [K6] etc. are mentioned.

Resin [K1] At least one monomer (a) (hereinafter sometimes referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and a ring having 2 to 4 carbon atoms A copolymer of a monomer (b) with an ether-like structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)"); resin [K2] (a) and (b) can be copolymerized with (a) Copolymer of monomer (c) (but different from (a) and (b)) (hereinafter sometimes referred to as "(c)"); resin [K3] Copolymer of (a) and (c); resin [K4] Resin for reacting (b) to the copolymer of (a) and (c); Resin [K5] Resin for reacting (a) to the copolymer of (b) and (c); Resin [K6] for (a) Resin which is reacted with the copolymer of (b) and (c), and then further reacted with carboxylic acid anhydride.

(a), specifically, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinyl benzoic acid, etc.; maleic acid, fumaric acid, etc. Oleic acid, Citraconic Acid, Mesaconic Acid, Itaconic Acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4, Unsaturation of 5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic acid, etc. Dicarboxylic acids; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2- 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- Bicyclic unsaturated compounds containing carboxyl groups such as methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, etc.; maleic anhydride, citrate Aconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6 -Unsaturated dicarboxylic anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; succinic acid mono[ Unsaturated mono[(( Meth) acryloxyalkyl] ester; α-(hydroxymethyl) acrylic acid is like an unsaturated acrylate containing hydroxyl and carboxyl groups in the same molecule.

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable from the point of copolymerization reactivity or the point of solubility to an alkaline aqueous solution of the resin obtained.

(b) means, 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 polymerizable compounds with ethylenically unsaturated bonds.

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

In this specification, "(meth)acrylic acid" means at least one kind selected from the group consisting of acrylic acid and methacrylic acid. Symbols such as "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

(b), for example, a monomer (b1) (hereinafter sometimes referred to as "(b1)") having an oxirane group and an ethylenically unsaturated bond, a monomer having an oxyethylene group and an ethylenically unsaturated bond, Monomer (b2) (hereinafter sometimes referred to as "(b2)"), monomer (b3) (hereinafter sometimes referred to as "(b3)") having a tetrahydrofuran group and an ethylenically unsaturated bond, and the like.

(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)" ), and a monomer (b1-2)) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-2)").

(b1-1), glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl (meth)acrylate, etc. Ethyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, alpha-methyl-o- -Vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2, 3-bis(glycidoxymethyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)benzene Ethylene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris(glycidoxymethyl)styrene, 2,3,5-tris(epoxymethyl)styrene Propyloxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris(glycidoxymethyl)styrene, 2,4,6-Tris(glycidoxymethyl)styrene, etc.

(b1-2), vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexene (for example, Celloxide 2000; manufactured by Daicel Co., Ltd.), (meth)acrylic acid 3,4-epoxycyclohexylmethyl ester (for example, Cyclomer A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer M100; manufactured by Daicel Co., Ltd.) , a compound represented by formula (II), a compound represented by formula (III), and the like.

[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 by a hydroxyl group; X ^a and X ^b represent Single bond, -R ^c -, *-R ^c -O-, *-R ^c -S- or *-R ^c -NH-; R ^c represents an alkanediyl group with 1 to 6 carbon atoms; * represents a combination with O bond key]

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

Examples of alkyl groups in which hydrogen atoms are substituted with hydroxyl groups include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, and 1-hydroxyl -1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc.

R ^a and R ^b preferably include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and particularly preferably a hydrogen atom and a methyl group.

Alkanediyl having 1 to 6 carbon atoms, such as methylene, ethylidene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane Alkane-1,5-diyl, hexane-1,6-diyl, etc.

Preferred examples of X ^a and X ^b include single bond, methylene group, ethylidene group, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, and particularly preferred examples include single bond, *-CH ₂ CH ₂ -O- (* indicates a bond with O).

As a compound represented by formula (II), the compound etc. which are represented by any one of formula (II-1) to 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) are preferred The compound represented by -15) is particularly preferably a compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15).

The compound represented by formula (III) includes the compound represented by any one of formula (III-1) to formula (III-15), and the like. Among them, formula (III-1), formula (III-3), formula (III-5), formula (III-7), formula (III-9) or formula (III-11) to formula (III) are preferred The compound represented by -15) is particularly preferably a compound represented by formula (III-1), formula (III-7), formula (III-9) or formula (III-15).

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

(b2), a monomer having an oxo group and a (meth)acryloyloxy group is particularly preferred. (b2), 3-methyl-3-methacryloyloxymethyl oxo, 3-methyl-3-acryloyloxymethyl oxo, 3-ethyl-3-methyl oxo Acryloyloxymethyloxygen, 3-ethyl-3-propenyloxymethyloxygen, 3-methyl-3-methacryloyloxyethyloxygen, 3-methyl-3- Acryloyloxyethyloxygen, 3-ethyl-3-methacryloyloxyethyloxygen, 3-ethyl-3-propenyloxyethyloxygen, and the like.

(b3), the monomer which has a tetrahydrofuranyl group and a (meth)acryloyloxy group is especially preferable. (b3), tetrahydrofuran methyl acrylate (for example, Viscoat #150, the product made by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofuran methyl methacrylate, etc. are mentioned specifically,.

(b), (b1) is preferable from the viewpoint that the reliability of the heat resistance, chemical resistance, etc. of the obtained color filter can be improved. Moreover, (b1-2) is especially preferable from the point which is excellent in the storage stability of a colored curable resin composition.

(c), for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, tertiary butyl (meth)acrylate, tributyl (meth)acrylate Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[ ^5.2.1.02.6 ]decane-8-ester (meth)acrylate (in this technical field, commonly used The name is "dicyclopentyl (meth)acrylate". In addition, it may be called "tricyclodecyl (meth)acrylate"), (meth)acrylate tricyclo[5.2.1.0 ^2.6 ]decene -8-ester (in this technical field, the common name is called "dicyclopentenyl (meth)acrylate"), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate , adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzene (meth)acrylate (Meth)acrylates such as methyl ester; (meth)acrylates containing hydroxyl groups such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.; Dicarboxylic acid diesters of ethyl ester, diethyl fumarate, diethyl itconate, etc.; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2- 2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2- alkene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2. 1] Hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5, 6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxy bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2 -ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tertiary butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxy ylcarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tertiary butoxycarbonyl)bicyclo[2.2.1 ] Hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N-phenylmaleimide, N -Cyclohexyl maleimide, N-benzyl maleimide, N-succinimide group -3-Maleimide benzoate, N-succinimide-4-maleimide butyrate, N-succinimide-6-malei Dicarbonyl imidate, N-succinimidyl hexanoate, N-succinimidyl-3-maleimidopropionate, N-(9-acridyl)maleimide, etc. Amine derivatives; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride , vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

Among these, from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyltoluene, benzyl (meth)acrylate, and tricyclo[5.2.1.0 ^2.6 ]decane (meth)acrylate are preferred Alkyl-8-ester, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]heptane -2-ene.

In the resin [K1], the ratio of the structural unit derived from each of the total structural units constituting the resin [K1] is preferably: the structural unit derived from (a); 2 to 60 mol %

Structural unit from (b); 40 to 98 mol%

Especially preferred: structural units from (a); 10 to 50 mol%

Structural unit from (b); 50 to 90 mol%.

When the ratio of the structural unit of the resin [K1] is in the above-mentioned range, the storage stability of the colored curable resin composition, the developability when forming the colored pattern, and the solvent resistance of the obtained color filter are reduced. Tendency to excellence.

For resin [K1], for example, reference can be made to the method described in the document "Experimental Methods for Polymer Synthesis" (Otsu Takayuki Publishing House Chemical Doujin Co., Ltd. 1st Edition, March 1, 1972) and the methods described in this document. Manufactured from the cited references.

Specifically, the predetermined amounts of (a) and (b), a polymerization initiator, a solvent, and the like are put into a reaction vessel, for example, nitrogen gas is used to replace oxygen gas to form a deoxidized atmosphere, and heating is performed while stirring. and methods of keeping warm. The above-mentioned polymerization initiator, solvent, etc. are not particularly limited, and those generally used in this field can be used. Examples of polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxides As the solvent (E) of the colored curable resin composition of the present invention, the solvent (E) of the colored curable resin composition of the present invention, etc., may be used as long as it can dissolve each monomer.

The obtained copolymer can be directly used as the solution after the reaction, or as the solution after concentration or dilution, or as the solid (powder) taken out by methods such as reprecipitation. In particular, by using the solvent contained in the colored curable resin composition of the present invention as the solvent during the polymerization, the solution after the reaction can be used as it is in the preparation of the colored curable resin composition of the present invention, so that the simplification can be achieved. The manufacturing process of the colored curable resin composition of this invention.

In the resin [K2], the ratio of the structural unit derived from each of the total structural units constituting the resin [K2] is preferably: the structural unit derived from (a); 2 to 45 mol%

Structural unit from (b); 2 to 95 mol%

Structural unit from (c); 1 to 65 mol%

Especially preferred: structural units from (a); 5 to 40 mol %

Structural unit from (b); 5 to 80 mol%

Structural unit from (c); 5 to 60 mol%.

When the ratio of the structural unit of the resin [K2] is within the above-mentioned range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance, heat resistance and The mechanical strength tends to be excellent.

The resin [K2] can be produced, for example, in the same manner as the method described as the production method of the resin [K1].

In the resin [K3], the ratio of the structural unit derived from each of the total structural units constituting the resin [K3] is preferably: the structural unit derived from (a); 2 to 60 mol %

Structural unit from (c); 40 to 98 mol%

Especially preferred: structural units from (a); 10 to 50 mol%

Structural unit from (c); 50 to 90 mol%.

The resin [K3] can be produced, for example, in the same manner as the method described as the production method of the resin [K1].

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

First, the copolymer of (a) and (c) was produced in the same manner as the method described as the production method of the resin [K1]. In this case, the ratio of the structural unit derived from each is preferably the same ratio as that listed in the resin [K3].

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

Next, after the production of the copolymer of (a) and (c), the ambient gas in the flask was replaced from nitrogen to air, and the reaction catalyst (tri(b), carboxylic acid or carboxylic acid anhydride and cyclic ether) was replaced with air. dimethylaminomethyl)phenol, etc.), a polymerization inhibitor (hydroquinone, etc.), etc., are put into a flask, and the resin [K4] can be produced by reacting at 60 to 130° C. for 1 to 10 hours, for example.

The amount of (b) is preferably 5 to 80 mol, more preferably 10 to 75 mol, relative to 100 mol of (a). By setting this range, the storage stability of the colored curable resin composition, the developability during pattern formation, and the balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern can be improved. tendency. Since the cyclic ether has high reactivity and does not easily remain unreacted (b), the (b) used for the resin [K4] is preferably (b1), more preferably (b1-1).

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

The reaction conditions such as the charging method, the reaction temperature, and the time can be appropriately adjusted in consideration of the production facility, the amount of heat generated by the polymerization, and the like. Similar to the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

Resin [K5], in the first stage, obtained the copolymer of (b) and (c) in the same manner as in the production method of the above-mentioned resin [K1]. In the same way as above, the obtained copolymer can be directly used as the solution after the reaction, or as a concentrated or diluted solution, or as a solid (powder) extracted by methods such as reprecipitation.

The ratios of the structural units derived from (b) and (c), relative to the total moles of all the structural units constituting the aforementioned copolymer, are preferably respectively: structural units derived from (b); 5 to 95 mol%

Structural unit from (c); 5 to 95 mol%

Especially preferred: structural units from (b); 10 to 90 mol%

Structural unit from (c); 10 to 90 mol%.

Furthermore, under the same conditions as in the production method of resin [K4], the carboxylic acid or carboxylic acid anhydride contained in (a) is allowed to react with the ring derived from (b) contained in the copolymer of (b) and (c). form ether, thereby obtaining resin [K5].

The amount of (a) to be reacted to the aforementioned copolymer is preferably 5 to 80 mol relative to 100 mol of (b). Since the cyclic ether has high reactivity and is unlikely to remain unreacted (b), the (b) used for the resin [K5] is preferably (b1), more preferably (b1-1).

Resin [K6] is the resin which made carboxylic anhydride react with resin [K5] further. The 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.

Carboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydro Phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene Anhydride etc. The amount of the carboxylic anhydride to be used is preferably 0.5 to 1 mol relative to 1 mol of the amount of (a).

Specific examples of the resin (B) include (meth)acrylic acid 3,4-epoxycyclohexylmethyl ester/(meth)acrylic acid copolymer, (meth)acrylic acid 3,4-epoxytricyclo[ 5.2.1.0 ^2.6 ] Resin [K1] of decyl ester/(meth)acrylic acid copolymer, etc.; Glycidyl meth)acrylate/styrene/(meth)acrylic acid copolymer, (meth)acrylic acid 3,4-epoxytricyclo[ ^5.2.1.02.6 ]decyl ester/(meth)acrylic acid/N -Cyclohexylmaleimide copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[ ^5.2.1.02.6 ]decyl ester/(meth)acrylic acid/vinyltoluene copolymer, 3- Resin [K2] of methyl-3-(meth)acryloyloxymethyloxy/(meth)acrylic acid/styrene copolymer; benzyl (meth)acrylate/(meth)acrylic acid copolymer resin [K3], such as styrene/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(meth)acrylic acid tricyclodecyl/(meth)acrylic acid copolymer, etc.; ) Resin in which glycidyl acrylate is added to benzyl (meth)acrylate/(meth)acrylic acid copolymer, and glycidyl (meth)acrylate is added to tricyclodecyl (meth)acrylate /Styrene/(meth)acrylic copolymer resin, adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylate Resin [K4] of acrylic copolymer resin, etc.; resin of (meth)acrylic acid reacting with tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate copolymer, (meth)acrylic acid Resin [K5] in which acrylic acid is reacted with a copolymer of tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate, etc.; Resin [K6] etc., such as the resin obtained by the copolymer of tricyclodecyl acrylate/(meth)acrylate glycidyl, further reacted with tetrahydrophthalic anhydride.

Resin (B), 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] A kind of group. In the case of such resins, the developability of the colored curable resin composition is excellent. Resin [K2] is more preferable from a viewpoint of the adhesiveness of a colored pattern and a board|substrate.

The polystyrene-converted weight average molecular weight (Mw) of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, more preferably 5,000 to 30,000. When the weight-average molecular weight (Mw) is in the aforementioned range, the hardness of the coating film formed from the coloring curable resin composition containing it is improved, the residual film rate is also high, the solubility of the unexposed part to the developing solution is good, and the coloring pattern is obtained. The resolution 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, particularly preferably 1.2 to 4.

The acid value of the resin (B) is preferably 50 to 170 mg-KOH/g, more preferably 60 to 150 mg-KOH/g, 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 determined by, for example, titration using an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably from 7 to 65 mass %, more preferably from 13 to 60 mass %, more preferably from 17 to 55 mass % with respect to the total amount of solid content. When the content of the resin (B) is within the aforementioned range, a colored pattern can be formed, and the resolution and residual film ratio of the colored pattern tend to improve.

<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). As a polymerizable compound (C), the compound etc. which have a polymerizable ethylenically unsaturated bond are mentioned, Preferably it is a (meth)acrylate compound.

The polymerizable compound having one ethylenically unsaturated bond includes nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc., and (a), (b) and (c) above.

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

The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of the polymerizable compound include trimethylolpropane tri(meth)acrylate, neotaerythritol tri(meth)acrylate, neotaerythritol tetra(meth)acrylate, and penta(meth)acrylate. Dipiveaerythritol acrylate, Dipiveaerythritol hexa(meth)acrylate, Tripivalerythritol octa(meth)acrylate, Tripivalerythritol hepta(meth)acrylate, Ten(meth)acrylate base) tetrapiotaerythritol acrylate, tetrapiotaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, denatured with ethylene glycol Tetra(meth)acrylate neotaerythritol, ethylene glycol denatured hexa(meth)acrylate dipeutaerythritol, propylene glycol denatured tetra(meth)acrylate neotaerythritol, propylene glycol denatured Denatured hexa(meth)acrylate dipivoerythritol, caprolactone denatured tetra(meth)acrylate neotaerythritol, caprolactone denatured hexa(meth)acrylate dipivoerythritol Esters, etc., among them, dipeutaerythritol penta(meth)acrylate and dipeutaerythritol hexa(meth)acrylate are preferable.

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

The content of the polymerizable compound (C) is preferably from 7 to 65 mass %, more preferably from 13 to 60 mass %, more preferably from 17 to 55 mass % with respect to the total amount of solid content.

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

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

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. by the action of light or heat to initiate polymerization, and generally known polymerization initiators can be used. .

The polymerization initiator (D) includes an O-acyl oxime compound, an alkyl phenyl ketone compound, a bisimidazole compound, a triazine compound, an acyl phosphine oxide compound, and the like.

The aforementioned O-acyl oxime compound is a compound having a structure represented by formula (d1). Hereinafter, * represents a bond key.

The aforementioned O-acyl oxime compound includes N-benzyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzyloxy-1 -1-(4-Phenylthiophenyl)octan-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentane Propane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]ethyl Alkyl-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolane ylmethyloxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methyl) benzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyloxy-1-[9-ethyl-6-(2- methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercially available products such as Irgacure OXE01 and OXE02 (the above are manufactured by BASF Co., Ltd.) and N-1919 (manufactured by ADEKA Co., Ltd.) can also be used. Among them, the O-acyl oxime compound is preferably selected from N-benzyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzyl Ethyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine and N-benzyloxy-1-(4-phenylthiophenyl)-3 -At least one of the group consisting of cyclopentylpropane-1-one-2-imine, particularly preferably N-benzyloxy-1-(4-phenylthiophenyl)octane- 1-keto-2-imine. In the case of such an O-acyl oxime compound, there is a tendency that a color filter with high brightness can be obtained.

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

Compounds having a structure represented by formula (d2) include 2-methyl-2-N-morpholinyl-1-(4-methylthiophenyl)propan-1-one, 2- Dimethylamino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylbenzene yl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. Commercially available products such as Irgacure 369, 907, and 379 (the above are manufactured by BASF Corporation) can also be used.

Compounds having a structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-( 2-Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one The oligomer, α, α-diethoxyacetophenone, benzophenone (benzil) dimethyl ketal and so on.

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

The aforementioned bisimidazole compound is, for example, a compound represented by the formula (d5).

[In formula (d5), R ¹³ to R ¹⁸ represent optionally substituted aryl groups having 6 to 10 carbon atoms]

Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, and the like, and a phenyl group is preferably used.

The substituents include halogen atoms, alkoxy groups having 1 to 4 carbon atoms, and the like. A fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned as a halogen atom, Preferably a chlorine atom is mentioned. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and the like, and a methoxy group is preferably used.

Bisimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,3-dichlorophenyl) Phenyl)-4,4',5,5'-tetraphenylbisimidazole (refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'-bis(2- Chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)bisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'- Tetrakis(dialkoxyphenyl)bisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)bisimidazole (refer to Japan Japanese Patent Publication No. Sho 48-38403, Japanese Patent Publication No. Sho 62-174204, etc.), imidazole compounds in which the phenyl group at the 4,4', 5,5'-position is substituted with a carboalkoxy group (refer to Japanese Patent Laid-Open No. 7 - Bulletin No. 10913, etc.) and so on. Among them, compounds represented by the following formulae and mixtures thereof are preferred.

The aforementioned triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) base)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-sunenyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2- (5-Methylfuran-2-yl)ethylene]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethylene Ethyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethylene] -1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine Wait.

As said acylphosphine oxide compound, 2,4,6- trimethylbenzyldiphenylphosphine oxide etc. are mentioned.

Furthermore, the polymerization initiator (D) includes benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; diphenyl ketone, o-benzyl benzoic acid Methyl ester, 4-phenyldiphenyl ketone, 4-benzyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tertiary butylperoxycarbonyl) Diphenyl ketone compounds such as benzophenone, 2,4,6-trimethyl benzophenone, etc.; 9,10-phenanthrenequinone (9,10-Phenanthrenequinone), 2-ethylanthraquinone, camphorquinone, etc. The quinone compound; 10-butyl-2-chloroacridone, benzophenone (benzil), methyl phenylglyoxylate, titanocene (Titanocene) compound and so on.

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

The polymerization initiator (D) preferably contains at least one selected from the group consisting of alkyl phenyl ketone compounds, triazine compounds, acylphosphine oxide compounds, O-acyl oxime compounds and bisimidazole compounds The polymerization initiator is particularly preferably a polymerization initiator containing an O-acyl oxime compound.

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

<Polymerization Initiating Auxiliary (D1)>

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

The polymerization initiator (D1) includes an amine compound, an alkoxyanthracene compound, a thioxanthone compound, a carboxylic acid compound, and the like.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoate. Isoamyl aminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4 '-bis(dimethylamino)diphenyl ketone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)diphenyl ketone, 4,4'-bis (Ethylmethylamino)diphenyl ketone, etc. Among them, 4,4'-bis(diethylamino)diphenyl ketone is preferable. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

The aforementioned alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl- 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

The aforementioned thioxanthone compound includes 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 1- Chloro-4-propoxythioxanthone, etc.

The aforementioned carboxylic acid compound includes phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methylphenylthioacetic acid Oxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid , N-naphthylglycine, naphthyloxyacetic acid, etc.

When these polymerization initiators (D1) are used, the content is preferably 0.1 to 30 parts by mass, particularly preferably 1 to 20 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). parts by mass. 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 be improved.

<Solvent (E)>

The solvent (E) is not particularly limited, and those commonly used in this field can be used. Examples of the solvent (E) include ester solvents (solvents containing -COO- and no -O- in the molecule), ether solvents (solvents containing -O- and no -COO- in the molecules), ethers Ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- and no -COO- in the molecule), alcohol solvent (containing OH in the molecule and not - O-, -CO- and -COO- solvents), aromatic hydrocarbon solvents, amide solvents and dimethyl methylene, etc.

The ester solvent includes methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, Butyl Propionate, Isopropyl Butyrate, Ethyl Butyrate, Butyrate, Methyl Pyruvate, Ethyl Pyruvate, Propyl Pyruvate, Methyl Acetate, Ethyl Acetate, Cyclohexyl Alcohol acetate and γ-butyrolactone, etc.

The ether solvent includes ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethyl ether. 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-methyl butanol, tetrahydrofuran , tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol diethyl ether Butyl ether, methoxybenzene, ethoxybenzene and methyl methoxybenzene, etc.

The ether ester solvent includes methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-methoxypropionate. Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate ester, 2-methoxypropionate propyl, 2-ethoxypropionate methyl ester, 2-ethoxypropionate ethyl ester, 2-methoxy-2-methyl propionate methyl ester, 2-ethyl propionate Ethyl oxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate ester and dipropylene glycol methyl ether acetate, etc.

Ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone ketone, cyclopentanone, cyclohexanone and isophorone, etc.

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

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

The amide solvent includes N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

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

Among them, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol are preferred 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, N-methylpyrrolidone, etc., especially 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, 3-ethoxyethyl propionate and N-methylpyrrolidone.

The content of the solvent (E) is preferably 70 to 95% by mass, particularly preferably 75 to 92% by mass, with respect to the total amount of the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, particularly preferably 8 to 25% by mass. When the content rate of the solvent (E) is within the above-mentioned range, the flatness at the time of coating the colored curable resin composition is good, and the color density is not insufficient when the color filter is formed, so that the display characteristics become good. tendency.

<Leveling agent (F)>

The leveling agent (F) includes polysiloxane-based surfactants, fluorine-based surfactants, and polysiloxane-based surfactants having fluorine atoms. These may have a polymerizable group in the side chain.

The polysiloxane-based surfactants include those having a siloxane bond in the molecule, and the like. Specifically, Toray Silicone DC3PA, the same SH7PA, the same DC11PA, the same SH21PA, the same SH28PA, the same SH29PA, the same SH30PA, the same SH8400 (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, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.), etc.

The aforementioned fluorine-based surfactants include surfactants having a fluorocarbon chain in the molecule, and the like. Specifically, Fluorad (registered trademark) FC430, the same FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, the same F171, the same F172, the same F173, the same F177, the same F183, the same F554, the same R30 , same as RS-718-K (manufactured by DIC Co., Ltd.), F-Top (registered trademark) EF301, same as EF303, same as EF351, same as EF352 (manufactured by Mitsubishi Material Electronics Chemicals Co., Ltd.), Surflon (registered trademark) S381, The same as S382, the same as SC101, the same as SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Institute).

The above-mentioned polysiloxane-based surfactant having a fluorine atom includes a surfactant having a siloxane bond and a fluorocarbon chain in the molecule, and the like. Specifically, Megafac (registered trademark) R08, the same BL20, the same F475, the same F477, and the same F443 (manufactured by DIC Co., Ltd.), etc. are mentioned.

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

<Antioxidant (H)>

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

Examples of the aforementioned phenolic antioxidant include Irganox 1010 (Irganox 1010: neopentaerythritol tetrakis[3-(3,5-bis(tertiary butyl)-4-hydroxyphenyl)propionate], BASF Co., Ltd. Company), Irganox 1076 (Irganox 1076: octadecyl-3-(3,5-bis(tertiary butyl)-4-hydroxyphenyl)propionate], BASF Co., Ltd.), Irganox 1330 (Irganox 1330: 3,3',3",5,5',5"-hexa(tertiary butyl)-a,a',a"-(trimethylbenzene-2,4,6-triyl)tris - p-cresol, manufactured by BASF Co., Ltd.), Irganox 3114 (Irganox 3114: 1,3,5-tris(3,5-bis(tertiary butyl)-4-hydroxybenzyl)-1,3, 5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Co., Ltd.), Irganox 3790 (Irganox 3790: 1,3,5-tris((4-tertiarybutyl- 3-Hydroxy-2,6-xylyl)methyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Co., Ltd.), Irganox 1035 (Irganox 1035: thiodieneethylbis[3-(3,5-bis(tert-butyl)-4-hydroxyphenyl)propionate], manufactured by BASF Co., Ltd.), Irganox 1135 (Irganox 1135: Phenylpropionic 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, manufactured by BASF Corporation), Irganox 3125 (Irganox3125, manufactured by BASF Corporation), Irganox 565 (Irganox 565: 2,4-bis(n-octylthio) -6-(4-Hydroxy-3,5-bis(tertiary butylanilino)-1,3,5-triazine, manufactured by BASF Co., Ltd.), ADK Stab AO-80 (ADK Stab AO-80: 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2, 4,8,10-Tetraoxaspiro(5,5)undecane, manufactured by ADEKA Co., Ltd.), Sumilizer BHT (Sumilizer BHT: manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GA-80 (Sumilizer GA-80: Sumitomo Chemical Co., Ltd.), Sumilizer GS (Sumilizer GS: Sumitomo Chemical Co., Ltd.) Co., Ltd.), Cyanox 1790 (Cyanox 1790: Cytec Co., Ltd.), and vitamin E (Eisai Co., Ltd.), etc.

The aforementioned phosphorus-based antioxidants include Irgafos 168 (Irgafos 168: tris(2,4-bis(tertiary butyl)phenyl) phosphite, manufactured by BASF Co., Ltd.), Irgafos 12 (Irgafos 12: tris[ 2-[[2,4,8,10-Tetrakis(tertiarybutyl)dibenzo[d,f][1,3,2]dioxaphosphoran-6-yl]oxy]ethyl]amine , 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. ), ADK Stab 329K (manufactured by ADEKA Co., Ltd.), ADK Stab PEP36 (manufactured by ADEKA Co., Ltd.), ADK Stab PEP-8 (manufactured by ADEKA Co., Ltd.), Sandstab P-EPQ (manufactured by Clariant Co., Ltd.), Weston 618 ( Weston 618 (manufactured by GE), Weston 619G (Weston 619G, manufactured by GE), Ultranox 626 (Ultranox 626, manufactured by GE), and Sumilizer GP (Sumilizer GP: 6-[3-(3-tertiarybutyl-4) -Hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra(tertiarybutyl)dibenzo[d,f][1,3,2]dioxaphospha Heptane) (manufactured by Sumitomo Chemical Co., Ltd.), etc.

The aforementioned sulfur-based antioxidants include dilauryl thiodipropionate, dialkyl thiodipropionate compounds such as dimyristyl or distearyl, and tetrakis[methylene(3-dodecyl sulfide]. β-Alkyl mercaptopropionate compounds of polyhydric alcohols such as methane and the like.

<Other ingredients>

The colored curable resin composition of the present invention may optionally contain additives generally known in the technical field such as fillers, other polymer compounds, adhesion promoters, light stabilizers, and chain transfer agents.

<Method for producing colored curable resin composition>

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

When a pigment (Ab) is contained, it is preferable to mix with a part or all of the solvent (E) in advance, and to disperse|distribute using a bead mill etc. until the average particle diameter of a pigment becomes 0.2 micrometer or less. At this time, a part or all of the said pigment dispersing agent and resin (B) can be mix|blended as needed. Then, the remaining components are mixed with the pigment dispersion liquid thus obtained so as to have a predetermined concentration, whereby the intended coloring curable resin composition can be prepared.

About a coloring agent (A), it is preferable to prepare a solution by dissolving a part or all of the dye in the solvent (E) in advance. Preferably, the solution is filtered through a filter having a pore size of about 0.01 to 1 μm.

Preferably, the mixed colored curable resin composition is filtered with a filter having a pore size of about 0.01 to 10 μm.

<Manufacturing method of color filter>

A colored pattern can be produced from the colored curable resin composition of the present invention. As the manufacturing method of this coloring pattern, a lithography method, an inkjet method, a printing method, etc. are mentioned, Preferably, a lithography method is mentioned.

The lithography method is a method of applying the coloring curable resin composition to a substrate, drying it to form a coloring composition layer, and exposing the coloring composition layer through a photomask and developing the coloring composition layer. In the lithography method, a colored coating film of the cured product of the colored composition layer described above can be formed without using a photomask and/or without performing development during exposure. The colored pattern or colored coating film thus formed is the color filter of the present invention.

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

The substrate can be used: quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass coated with silica on the surface, etc.; or polycarbonate, polymethyl methacrylate, polymethyl methacrylate Resin plates such as ethylene phthalate; silicon; or those with aluminum, silver, silver/copper/palladium alloy thin films, etc. formed on the aforementioned substrate. On these substrates, other color filter layers, resin layers, transistors, circuits, and the like may be formed. The formation of pixels of various colors by lithography can be performed under general or conventional apparatus or conditions. For example, it can be produced as follows.

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

The coating method includes spin coating, slit coating, slit and spin coating, and the like.

The temperature during heating and drying is preferably 30 to 120°C, more preferably 50 to 110°C, and the heating time is preferably 10 seconds to 60 minutes, particularly preferably 30 seconds to 30 minutes.

When drying under reduced pressure, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150Pa.

The film thickness of the coloring composition layer is not particularly limited, and can be appropriately selected according to the film thickness of the intended color filter.

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

The light source used for exposure is preferably a light source that emits light with a wavelength of 250 to 450 nm. For example, the light below 350nm can be removed by using a filter that removes this wavelength region, or the light around 436nm, 408nm, and 365nm can be selectively selected using a bandpass filter that captures these wavelength regions to capture. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned as a light source.

Since the entire exposure surface can be uniformly irradiated with parallel light, or the mask and the substrate on which the coloring composition layer is formed can be accurately aligned, it is preferable to use a mask aligner, a stepper, or the like for exposure. device.

A colored pattern is formed on the substrate by contacting the exposed colored composition layer with a developing solution for development. By developing, the unexposed portion of the colored composition layer is dissolved in a developing solution and removed. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, particularly preferably 0.03 to 5% by mass. Furthermore, the developer may contain a surfactant. The developing method may be any of the paddle method, the immersion method, and the spray method. In addition, the substrate can be inclined at any angle during development. After development, it is preferable to wash with water.

In addition, it is preferable to post-bake the obtained colored pattern. The post-baking temperature is preferably 150 to 250°C, particularly preferably 160 to 235°C. The post-baking time is preferably 1 to 120 minutes, particularly preferably 10 to 60 minutes.

With the colored curable resin composition of the present invention, a high-contrast color filter can be produced. This color filter is a color filter used as a display device (liquid crystal display device, organic EL device, electronic paper, etc.) and a solid-state imaging element.

[Example]

The colored curable resin composition of the present invention will be described in more detail below by way of examples. "%" and "part" in the example are mass % and mass part unless otherwise specified.

[Synthesis Example 1: Synthesis of Triarylmethane Colorant (A-I-18)]

The following reactions were carried out in a 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 the flask equipped with a cooling pipe and a stirring device, the mixed solution was ice-cooled. Under ice-cooling, 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added a little at a time for 30 minutes, followed by stirring for 1 hour while warming up to room temperature. 10.4 parts of 4,4'- difluorodiphenyl ketone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the reaction liquid in small portions, and the mixture was stirred at room temperature for 24 hours. After adding the reaction solution to 200 parts of ice water a little at a time, it was left to stand at room temperature for 15 hours, and water was removed by decantation to obtain a viscous solid as a residue. After adding 60 parts of methanol to the viscous solid, the mixture was stirred at room temperature for 15 hours. After filtering the precipitated solid, it was purified by chromatography. The purified pale yellow solid was dried under reduced pressure at 60°C to obtain 9.8 parts of a compound represented by formula (C-I-18).

The following reactions were carried out in a nitrogen atmosphere. After adding 8.2 parts of the compound represented by the formula (B-I-7), 10 parts of the compound represented by the formula (C-I-18), and 20 parts of toluene to a flask equipped with a cooling pipe and a stirring device, 12.2 parts of phosphorus oxychloride was added portion, and stirred at 95 to 100 °C for 3 hours. Then, after cooling the reaction mixture to room temperature, it was diluted with 170 parts of isopropanol. Next, after pouring the diluted reaction solution into 300 parts of saturated brine, 100 parts of toluene was added, followed by stirring for 30 minutes. Then, stirring was stopped, and the organic layer was separated from the aqueous layer by standing for 30 minutes. After removing the aqueous layer by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of Glauber's salt was added to the organic layer, followed by stirring for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was solvent-distilled with an evaporator, and the blue-purple solid was obtained. Then, the blue-violet solid was dried under reduced pressure at 60°C to obtain 18.4 parts of the compound represented by the formula (A-II-18).

The following reactions were carried out in a 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, the mixture was stirred at room temperature for 30 minutes to prepare a blue solution. Next, 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.

53 parts of water were put into a beaker, then 11.8 parts of Keggin-type phosphotungstic acid (manufactured by Aldrich) and 53 parts of methanol were put into the water, and mixed at room temperature to prepare a phosphotungstic acid solution.

The obtained phosphotungstic acid solution was dropped into the previously prepared reaction solution over 1 hour. Then, after stirring at room temperature for 30 minutes, it was filtered to obtain a blue solid. The obtained blue solid was added to 200 parts of methanol and dispersed for 1 hour, and then the filtration operation was repeated twice. After the blue solid obtained by this operation was put into 200 parts of water and dispersed for 1 hour, the filtration operation was repeated twice. The blue solid obtained by this operation was dried at 60 degreeC under reduced pressure, and 17.1 parts of triarylmethane colorants (A-I-18) represented by formula (A-I-18) were obtained.

[Synthesis Example 2: Synthesis of Dibenzopyran Dye (1-38)]

20 parts of the compound represented by the 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 added to 110 °C was stirred for 6 hours. After cooling the obtained reaction solution to room temperature, it was added to a mixed solution of 800 parts of water and 50 parts of 35% by weight hydrochloric acid, and stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystal was obtained as a residue of suction filtration, and then dried to obtain a dibenzopyran dye (1-38) represented by the formula (1-38).

[Synthesis Example 3: Synthesis of Resin B1]

In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, nitrogen gas was allowed to flow in an appropriate amount to form a nitrogen atmosphere, 305 parts of ethyl lactate was charged, and the mixture was heated to 70° C. while stirring and kept at the temperature. Next, 46 parts of acrylic acid and 3,4-epoxy tricyclo[5.2.1.0 ^2.6 ]decyl acrylate (in a molar ratio of 50:50) were mixed with the compound represented by the formula (I-1) and the compound represented by the formula (II) -1) 240 parts of compounds represented by ethyl lactate were dissolved in 185 parts of ethyl lactate to prepare a solution, and using a dropping funnel, the solution was dropped into a flask kept at 70°C for 4 hours.

On the other hand, a solution obtained by dissolving 30 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator in 225 parts of ethyl lactate over 4 hours using another dropping funnel Drop into the flask. After finishing the dropping of the polymerization initiator solution, it was kept at 70° C. for 4 hours, and then cooled to room temperature to obtain a weight-average molecular weight (Mw) of 9.1×10 ³ , a degree of dispersion of 2.1, a solid content of 26% by mass, and a solid Resin B1 solution with component acid value of 120 mg-KOH/g. Resin B1 has the structural unit shown below.

[Synthesis Example 4: Synthesis of Resin B2]

In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, nitrogen gas was allowed to flow in an appropriate amount to form a nitrogen atmosphere, 371 parts of propylene glycol monomethyl ether acetate was charged, and the mixture was heated to 85°C while stirring. Next, 54 parts of acrylic acid and 3,4-epoxy tricyclo[5.2.1.0 ^2.6 ]decyl acrylate (in a molar ratio of 50:50) were mixed with the compound represented by the formula (I-1) and the compound represented by the formula (II- 1) A mixed solution of 225 parts of the compound represented by), 81 parts of vinyltoluene (isomer mixture), and 80 parts of propylene glycol monomethyl ether acetate was added dropwise over 4 hours.

On the other hand, a mixed solution obtained by dissolving 30 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) in 160 parts of propylene glycol monomethyl ether acetate was dropped over 5 hours. After the dropping was completed, the same temperature was maintained 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 structural unit shown below.

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

Installation; K2479 (manufactured by Shimadzu Corporation)

String; SHIMADZU Shim-pack GPC-80M

Column temperature; 40℃

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0mL/min

detector; RI

Calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

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

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

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

[Preparation Example 2: Preparation of Dispersion Liquid (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 liquid (2 ).

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

(Preparation of Colored Curable Resin Composition)

In the parts shown in Table 3, mix: ‧Dispersion liquid (1) (containing 10% by mass of triarylmethane colorant (A-I-18)), ‧Dibenzopyran dye (1-38), ‧Anthracene Quinone dye (C.I. Solvent Blue 45; Savinyl Blue RS; manufactured by Clariant), ‧Dispersion (2), ‧(B) Resin: Resin B1, ‧(C) Polymerizable compound: Dipivalerythritol hexaacrylate ( Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.), ‧(D) Polymerization initiator: N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1 - Keto-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF Co., Ltd.), ‧(F) Leveling agent: polyether-denatured polysiloxane oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd. Company), ‧(E) solvent: ethyl lactate (EL), ‧(E) solvent: propylene glycol monomethyl ether acetate (PGMEA), and a colored curable resin composition was obtained.

<Creation of coloring patterns>

After applying the colored curable resin composition on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning) by spin coating, prebaking was performed at 100° C. for 3 minutes to obtain a colored composition layer. After standing to cool, the interval between the substrate on which the colored composition layer was formed and the mask made of quartz glass was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used to expose the light to 150 mJ/cm in the atmosphere. Light irradiation was performed at an exposure amount of ² (365 nm reference). As the photomask, one formed with a 100 μm line and space pattern was used. The light-irradiated coloring composition layer was immersed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 24°C for development, washed with water, and then carried out in an oven at 230°C A 30-minute post-bake results in a colored pattern.

<Film thickness measurement>

The film thickness of the obtained coloring pattern was measured using a film thickness measuring apparatus (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 4. In Table 4, the coloring agent (A) contained in the coloring curable resin composition obtained by mixing the parts shown in Table 3 is shown so that the total amount of the coloring agent (A) is 100. Convert the content of each component.

<Evaluation of chromaticity>

The obtained coloring pattern was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.) for spectroscopic measurement, and the xy chromaticity coordinates (x) in the XYZ colorimetric system of CIE were measured using the characteristic function of the C light source. , y) and the tristimulus value Y. The larger the Y value, the greater the brightness. The results are shown in Table 4.

<Comparative Evaluation>

Except that the photomask was not used during exposure, the same operation as the production of the colored pattern was performed to prepare a colored coating film. A contrast meter (CT-1; manufactured by Tsusaka Electric Co., Ltd., colorimeter BM-5A; manufactured by Topcon Corporation, light source: F-10, polarizing film; manufactured by Tsusaka Electric Co., Ltd.) was used for the obtained colored coating film. , set the blank value to 30000 and measure the comparison. The higher the contrast in the colored coating film, the higher the contrast in the colored pattern can also be considered. The results are shown in Table 4.

According to the coloring curable resin compositions of Examples 1 to 3 and Comparative Example 2, the chromaticity coordinates of y are 0.095, and the chromaticity coordinates of x are 0.136 to 0.139, and a coloring pattern close to the chromaticity can be obtained. Moreover, in Examples 1-3, compared with the comparative example 2, the coloring pattern of high brightness was obtained, and also the coloring coating film which showed high contrast was obtained.

According to the coloring curable resin compositions of Examples 4 to 8 and Comparative Examples 1 and 3, the chromaticity coordinate of y is 0.095, and the chromaticity coordinate of x is 0.150 to 0.153, and a coloring pattern close to the chromaticity can be obtained. Furthermore, in Examples 4 to 8, compared with Comparative Examples 1 and 3, a colored pattern with high brightness was obtained, and further, a colored coating film showing high contrast was obtained.

From the above, it can be seen 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 is excellent in the display properties, and can be used as a material for a liquid crystal display device.

Claims (5)

A coloring curable resin composition containing: a colorant, a resin, a polymerizable compound and a polymerization initiator; the colorant, containing: a triarylmethane colorant, a dibenzopyran dye, and an anthraquinone dye, The content rate of the said dibenzopyran dye in the said coloring agent is 1 mass % or more and 13.5 mass % or less. The colorable curable resin composition according to claim 1, wherein the content of the anthraquinone dye is 0.5 to 50 parts by mass relative to 100 parts by mass of the triarylmethane colorant. The colorable curable resin composition according to claim 2, wherein the content of the anthraquinone dye is 1.0 to 13.5 parts by mass relative to 100 parts by mass of the triarylmethane colorant. A color filter, which is formed of the coloring curable resin composition described in any one of claims 1 to 3 of the scope of application. A display device comprising the color filter described in item 4 of the patent application scope.