TWI691555B - Coloring curable resin composition - Google Patents

Abstract

The invention provides a color-curable resin composition capable of forming a color filter with good chemical resistance.

The color-curing resin composition of the present invention contains a blue dye, a resin, a polymerizable compound, a polymerization initiator, and a silsesquioxane compound. The colored curable resin composition preferably has a silsesquioxane compound content of 25 to 3000 parts by mass relative to 100 parts by mass of the blue dye.

Description

Coloring curable resin composition

The present invention relates to a color-curing resin composition.

Japanese Patent Laid-Open No. 2012-83652 describes a color-curable resin composition containing a blue dye, a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent.

The industry has demanded further improvement of the chemical resistance of color filters formed from the above-mentioned colored curable resin composition.

The present invention includes the following inventions.

[1] A color-curing resin composition containing a blue dye, a resin, a polymerizable compound, a polymerization initiator, and a silsesquioxane compound.

[2] The color-curable resin composition as described in [1], wherein the content of the silsesquioxane compound is 25 to 3000 parts by mass relative to 100 parts by mass of the blue dye.

[3] The color-curing resin composition as described in [1] or [2], wherein the blue dye includes a phthalocyanine dye, a triarylmethane dye, an anthraquinone dye, a cyanine dye, a porphyrin dye and At least one dye in the group consisting of thiazole dyes.

[4] The color-curable resin composition as described in [1] or [2], wherein the blue dye has at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen Atom anion compound.

[5] The color-curable resin composition as described in [1] or [2], wherein the blue dye contains the compound represented by formula (A-I).

[In formula (AI), [Y ² ] ^m- represents an arbitrary m-valent anion.

R ⁴¹ to R ⁴⁴ independently represent a hydrogen atom, a C 1-20 saturated hydrocarbon group which may be substituted, a group having an oxygen atom inserted between carbon atoms constituting an alkyl group having 2 to 20 carbon atoms, which may be substituted Aryl, or aralkyl which may be substituted. R ⁴¹ and R ⁴² may be bonded to form a ring with the nitrogen atoms to which they are bonded, and R ⁴³ and R ⁴⁴ may be bonded to form a ring with the nitrogen atoms to which they are bonded.

R ⁴⁵ to R ⁵² independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms, or a group having an oxygen atom inserted between carbon atoms constituting an alkyl group having 2 to 8 carbon atoms , Or R ⁴⁶ and R ⁵⁰ may be bonded to 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.

In the case where the compound represented by formula (A-I) contains a plurality of cations, the plurality of cations may have the same structure as each other or different structures.

m represents an arbitrary natural number]

[6] A color filter consisting of a color-hardenable tree as described in [1] or [2] Lipid composition.

[7] A display device including the color filter as described in [6].

The invention provides a color-curable resin composition capable of forming a color filter with good chemical resistance.

The color-curable resin composition of the present invention contains a blue dye, a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a silsesquioxane compound (H).

The color-curable resin composition of the present invention may further contain a solvent (E), a thiol compound (T), an antioxidant (G), a polymerization initiation aid (D1), and/or a leveling agent (F), wherein, Preferably, it contains a solvent (E), a thiol compound (T), an antioxidant (G), and/or a leveling agent (F).

<Blue dye (A)>

In the present invention, the blue dye refers to a dye having a maximum absorption wavelength in a range of 580 nm or more and 650 nm or less in a chloroform solution. The blue dye is preferably a dye having a maximum absorption wavelength in the range of 590 nm or more and 645 nm or less, and more preferably a dye having a maximum absorption wavelength in the range of 600 nm or more and 645 nm or less.

The blue dye in the present invention also includes compounds converted from dyes having a maximum absorption wavelength in the range of 580 nm or more and 650 nm or less, and having the following polyacid anions.

If the maximum absorption wavelength of the dye is within the range of 580 nm or more and 650 nm or less, the dye is not particularly limited, and known dyes can be used.

Examples of blue dyes include compounds classified as those having a hue in the Color Index (published by The Society of Dyers and Colourists) or dyeing notes (Dyeing Note) ) In the well-known dye. In addition, according to the chemical structure, phthalocyanine dye, diarylmethane dye, triarylmethane dye, anthraquinone dye, polymethine dye, azomethine dye, cyanine dye, porphyrin dye, thiazole Dyes and the like are preferably phthalocyanine dyes, triarylmethane dyes, anthraquinone dyes, cyanine dyes, porphyrin dyes and thiazole dyes.

Specifically, CI solvent blue 2, 4, 5, 14, 18, 35, 36, 37, 43, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 124, 128, 132, 136, 139; CI Acid Blue 1, 3, 5, 7, 9 , 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62 , 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90: 1, 91, 92, 93, 93: 1, 96, 99, 100, 102, 103, 104 , 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166 , 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 249, 256, 259, 267 , 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340; CI Direct Blue 1, 2, 3, 6, 8, 15, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 87, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CI disperse dyes such as CI disperse blue 1, 14, 56, 60, CI basic blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40 , 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89; CI mordant blue (Mordant blue) 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84, etc.

Examples of blue dyes include those described in International Publication No. 2012/128318, Korean Patent Publication No. 2014-0026284, Korean Patent Publication No. 2013-0111024, and Korean Patent Publication No. 2013-0062510. Color dye.

As the blue dye (A), a compound having an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and an oxygen atom can also be cited. Examples of the anions containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen include polyacid anions such as heteropolyacid anions having the element and homopolyacid anions having the element.

Examples of the anions of heteropolyacid or homopolyacid containing tungsten as an essential element include: Keggin type phosphotungstate ion α-[PW ₁₂ O ₄₀ ] ^3- and Dawson type Phosphotungstate ions α-[P ₂ W ₁₈ O ₆₂ ] ^6- , β-[P ₂ W ₁₈ O ₆₂ ] ^6- , Kejin-type tungstosilicate ions α-[SiW ₁₂ O ₄₀ ] ^4- , β- [SiW ₁₂ O ₄₀ ] ^4- , γ-[SiW ₁₂ O ₄₀ ] ^4- , and as another example, [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , α-[SiW ₉ O ₃₄ ] ^10- , γ-[SiW ₁₀ O ₃₆ ] ^8- , α-[SiW ₁₁ O ₃₉ ] ^8- , β-[SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- and mixtures of these. As anions of heteropolyacid or homopolyacid containing tungsten as an essential element, anions of phosphotungstic acid, silicotungstic acid and tungsten homopolyacid are preferred.

Moreover, it is also preferable to contain an anion containing at least one element selected from the group consisting of silicon and phosphorus and oxygen. Examples of the anion include SiO ₃ ^2- and PO ₄ ^3- .

Examples of the blue dye having an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and an oxygen atom include those having a cation selected from a phthalocyanine skeleton and a diarylmethane skeleton. At least one of the group consisting of a cation, a cation having a triarylmethane skeleton, a cation having an anthraquinone skeleton, a cation having an azomethine skeleton, a cation having a cyanine skeleton, and a cation having a porphyrin skeleton Compound of cation and the anion. Among the cations having a triarylmethane skeleton, at least one aryl group may be a heteroaryl group such as thiazole.

The blue dye is more preferably a compound represented by formula (A-I).

[In formula (A-1), [Y ² ] ^m- represents an arbitrary m-valent anion; R ⁴¹ to R ⁴⁴ independently represent a hydrogen atom, a C 1-20 saturated hydrocarbon group which may be substituted, and a carbon A group having an oxygen atom inserted between the carbon atoms of the alkyl group having 2 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 to form a ring with the nitrogen atoms to which they are bonded, and R ⁴³ and R ⁴⁴ may be bonded to form a ring with the nitrogen atoms to which they are bonded.

R ⁴⁵ to R ⁵² independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms, or a group having an oxygen atom inserted between carbon atoms constituting an alkyl group having 2 to 8 carbon atoms , Or R ⁴⁶ and R ⁵⁰ may be bonded to 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.

In the case where the compound represented by formula (A-I) contains a plurality of cations, the plurality of cations may have the same structure as each other or different structures.

m represents an arbitrary natural number]

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

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

[In formula (4), W ¹ and W ² each independently represent a group having two monovalent proton-donating substituents. M means boron or aluminum]

Examples of the group having two monovalent proton-donating substituents include a group obtained by releasing protons from each of the compounds having at least two monovalent proton-donating substituents (for example, hydroxyl group, carboxyl group, etc.). As the compound, catechol which may have a substituent, 2,3-dihydroxynaphthalene which may have a substituent, 2,2'-biphenol which may have a substituent, and 3- which may have a substituent Hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid which may have a substituent, 1-hydroxy-2-naphthoic acid which may have a substituent, binaphthol which may have a substituent, water which may have a substituent Salicylic acid, diphenyl glycolic acid which may have a substituent, or amygdalic acid which may have a substituent.

In each compound exemplified as the compound having at least two monovalent proton-donating substituents, examples of the substituent include saturated hydrocarbon groups (for example, alkyl groups, cycloalkyl groups, etc.), halogen atoms, hydroxyl groups, and amine groups. , Nitro, alkoxy, etc.

Examples of the salicylic acid which may have a substituent include: salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-methoxysalicylic acid, 3-nitrosalicylic acid Acid, 4-trifluoromethylsalicylic acid, 3,5-di-third-butylsalicylic acid, 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6 -Monosalicylic acid such as aminosalicylic acid; 3-hydroxysalicylic acid (2,3-dihydroxybenzoic acid), 4-hydroxysalicylic acid (2,4-dihydroxybenzoic acid), 5- Hydroxysalicylic acid (2,5-dihydroxybenzoic acid), 6-hydroxysalicylic acid (2,6-dihydroxybenzoic acid) and other monohydroxysalicylic acid; 4,5-dihydroxysalicylic acid, 4, 6-dihydroxysalicylic acid and other dihydroxysalicylic acid; 3-chlorosalicylic acid, 4-chlorosalicylic acid, 5-chlorosalicylic acid, 6-chlorosalicylic acid, 3-bromosalicylic acid, 4 -Bromosalicylic acid, 5-bromosalicylic acid, 6-bromosalicylic acid and other monohalogenated salicylic acid; 3,5-dichlorosalicylic acid, 3,5-dibromosalicylic acid, 3,5 -Dihalo-salicylic acid such as diiodosalicylic acid; trihalo-salicylic acid such as 3,5,6-trichlorosalicylic acid.

Examples of diphenyl glycolic acid which may have a substituent include:

Examples of amygdalic acid which may have a substituent include: [Chem. 5]

Wait.

Among the anions represented by formula (4), preferred anions include the anions represented by the following formula and anions (BC-1) to anions (BC-24) having the substituents described in Table 1. , And anions (BC-25) to anions (BC-28) represented by various formulas (BC-25), formula (BC-26), formula (BC-27) and formula (BC-28).

(M means boron or aluminum)

[Table 1]

(M means boron or aluminum)

[Chem 8]

(M means boron or aluminum)

(M means boron or aluminum)

(M means boron or aluminum)

As the anion represented by formula (4), anions (BC-1) and anions (BC- 2), anion (BC-3), anion (BC-25), anion (BC-26), anion (BC-27), more preferably anion (BC-1), anion (BC-2), anion ( BC-25), more preferably anions (BC-1) and anions (BC-2). Any one of these anions and the salt of the compound represented by formula (A-I) tend to have excellent solubility in an organic solvent.

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

[In formula (6), W ³ and W ⁴ each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or W ³ and W ⁴ together represent a fluorinated alkyldiyl group having 1 to 4 carbon atoms]

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

[Chem 13]

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

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

In the formulae (6), (7) and (9), the fluorinated alkyl 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 , -C(CF ₃ ) ₃ and so on.

In formulae (6) and (8), the fluorinated alkanediyl group having 1 to 4 carbon atoms is preferably a perfluoroalkanediyl group, and examples include: -CF ₂ -, -CF ₂ CF ₂ -, and -CF ₂ CF ₂ CF ₂ -, -C(CF ₃ ) ₂ -, -CF ₂ CF ₂ CF ₂ CF ₂ -, etc.

Examples of the anions represented by formula (6) (hereinafter referred to as "anions (6)") include the anions represented by various formulas (6-1) to (6-6) (hereinafter referred to as " Anions (6-1)" ~ "Anions (6-6)").

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

Examples of the anions represented by formula (8) (hereinafter referred to as "anions (8)") include the anions represented by various formulas (8-1) to (8-4) (hereinafter referred to as " Anions (8-1)" ~ "Anions (8-4)").

Examples of the anions represented by formula (9) (hereinafter referred to as "anions (9)") include the anions represented by various formulas (9-1) to (9-4) (hereinafter referred to as " Anions (9-1)" ~ "Anions (9-4)").

The [Y ² ] ^{m- is} preferably a fluorine-containing anion or a polyacid anion, more preferably an anion represented by formula (6), [PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , [SiW ₁₂ O ₄₀ ] ^4- or [W ₁₀ O ₃₂ ] ^4- , and further preferably anions represented by formula (6-1) to formula (6-5), [PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , particularly preferably the anion represented by formula (6-2), [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 in such a way that the charge of the anion [Y ² ] ^m- and the cation are equal. m is preferably a natural number of 1-10.

The saturated hydrocarbon groups having 1 to 20 carbon atoms represented by R ⁴¹ to R ⁴⁴ may be linear, branched, or cyclic. In addition, the saturated hydrocarbon group preferably has a carbon number of 1 to 10, more preferably a carbon number of 1 to 8, further preferably a carbon number of 1 to 6, and particularly preferably a carbon number of 1 to 4.

Examples of 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 groups; iso Branched chain alkyl such as propyl, isobutyl, 2-ethylhexyl. The carbon number of the linear or branched saturated hydrocarbon is preferably from 1 to 8, more preferably from 1 to 6, and even more preferably from 1 to 4.

In addition, the cyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. The carbon number of the cyclic saturated hydrocarbon group is preferably 3-10, more preferably 6-10.

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

[Chem 19]

Among the groups represented by R ⁴¹ to R ⁴⁴ , as a group in which an oxygen atom is inserted between methylene groups (carbon atoms) constituting an alkyl group having 2 to 20 carbon atoms, for example, a group represented by the following formula may be mentioned. In the following formula, * represents a bond with a nitrogen atom. Among them, the group having an oxygen atom inserted between the methylene groups constituting the alkyl group is preferably a group having 2 to 10 carbon atoms, and more preferably a group having 2 to 6 carbon atoms. The alkyl group into which an oxygen atom is inserted is preferably a linear alkyl group. In addition, the number of carbons between oxygen atoms is preferably 1 to 4, more preferably 2 to 3.

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

In addition, examples of the aryl group of R ⁴¹ to R ⁴⁴ include phenyl, naphthyl, tolyl, and the like.

Examples of the aryl group in the aralkyl group of R ⁴¹ to R ⁴⁴ include a phenyl group and a naphthyl group. As the aralkyl group, a bonding bond between the aryl group and an alkanediyl group is exemplified. base. The carbon number of the alkanediyl group is preferably 1 to 10, more preferably 1 to 5, and preferably a linear alkanediyl group. Specific examples of the alkanediyl group include methylene, ethylidene, propylidene, butanediyl, and glutaryl groups. Examples of the aralkyl group include benzyl, phenylethyl, Naphthylmethyl, naphthylethyl, etc.

Among the groups represented by R ⁴¹ to R ⁴⁴ , in the aryl group and the aralkyl group, examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, and an iodine atom; and carbon numbers such as a methoxy group and an ethoxy group 1 to 6 alkoxy groups; hydroxyl groups; methyl sulfonyl groups and other C 1-6 alkyl sulfonyl groups; methoxycarbonyl and ethoxycarbonyl groups and other C 2 to 6 alkoxycarbonyl groups.

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

Examples of the aralkyl group which may be substituted include a group obtained by bonding an alkylene group such as methylene group and ethylidene group to the bonding bond of the aryl group.

啉環、哌啶環、哌

環等6員環等。 As the ring formed by bonding R ⁴¹ and R ⁴² together with the nitrogen atoms bonded thereto, and the ring formed by bonding R ⁴³ and R ⁴⁴ together with the nitrogen atoms bonded thereto, there can be exemplified : 5-membered ring including pyrrolidine ring;

Porphyrin ring, piperidine ring, piper

Ring and other 6 member rings.

Regarding R ⁴¹ to R ⁴⁴ , in terms of ease of synthesis, it is preferably independently a C 1-20 saturated hydrocarbon group which may be substituted, an aryl group which may be substituted, or an aromatic group which may be substituted The alkyl group is more preferably a saturated hydrocarbon group independently having 1 to 8 carbon atoms or an optionally substituted aryl group represented by the following formula. In the following formula, * represents a bond with a nitrogen atom.

The saturated hydrocarbon group having 1 to 8 carbon atoms represented by R ⁴⁵ to R ⁵² may be linear, branched, or cyclic, and is preferably a chain. Examples of the saturated hydrocarbon groups having 1 to 8 carbon atoms for R ⁴⁵ to R ⁵² include the groups having 1 to 8 carbon atoms among the groups exemplified as the saturated hydrocarbon groups for R ⁴¹ to R ⁴⁴ . As a group in which an oxygen atom is inserted between the methylene group (carbon atom) constituting the alkyl group, an alkyl group having 2 to 8 carbon atoms is more preferable. The alkyl group into which the oxygen atom is inserted is preferably a linear alkyl group, and the number of carbons between oxygen atoms is preferably 1 to 4, more preferably 2 to 3. For example, the group represented by the following formula can be mentioned. In the following formula, * represents a bond with a carbon atom.

Regarding R ⁴⁵ to R ⁵² , in terms of ease of synthesis, it is preferably independently a hydrogen atom, a halogen atom, or a saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably independently a hydrogen atom, a methyl group Radical, fluorine atom or chlorine atom.

R ⁴⁶ and R ⁵⁰ may be bonded to 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 any of a single ring and a condensed ring, and examples thereof include phenyl, tolyl, xylyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, and triphenyl. 20 aromatic hydrocarbon groups.

Heteroaryl groups are substituents derived from aromatic heterocycles. The above-mentioned aromatic heterocyclic ring may be either a monocyclic ring or a condensed ring, preferably a 5-10 member ring, more preferably a 5-9 member ring.

唑環、吡唑環、 咪唑環、噻唑環等具有氮原子之5員環；呋喃環、噻吩環等具有氧原子或硫原子之5員環；吡啶環、嘧啶環、嗒

環、吡

環等具有氮原子之6員環等。作為縮合環之芳香族雜環，可列舉：吲哚環、苯并咪唑環、苯并噻唑環、喹啉環等具有氮原子之縮合環；苯并呋喃環等具有氧原子或硫原子之環等。作為可經取代之雜芳基，更佳為式(Ab2-x1)所表示之基。 Examples of monocyclic aromatic heterocycles include pyrrole rings,

5-membered ring with nitrogen atom such as azole ring, pyrazole ring, imidazole ring, thiazole ring; 5-membered ring with oxygen atom or sulfur atom such as furan ring, thiophene ring; pyridine ring, pyrimidine ring, ta

Ring, pyridine

Rings and other 6-membered rings with nitrogen atoms. Examples of the aromatic heterocyclic ring of the condensed ring include a condensed ring having a nitrogen atom such as an indole ring, a benzimidazole ring, a benzothiazole ring, and a quinoline ring; a ring having an oxygen atom or a sulfur atom such as a benzofuran ring Wait. The heteroaryl group which may be substituted is more preferably a group represented by the formula (Ab2-x1).

[Ring T ² represents an aromatic heterocyclic ring, preferably an aromatic heterocyclic ring having 2 to 9 carbon atoms.

R ⁵³ and R ⁵⁴ independently represent a C 1-20 saturated hydrocarbon group which may be substituted by a substituted or unsubstituted amine group or a halogen atom, and oxygen is inserted between carbon atoms constituting the C 2-20 alkyl group Atom group, aryl group which may be substituted, or aralkyl group which may 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 which may be substituted.

k1 represents 0 or 1.

* Indicates a bond with a carbocation] Furthermore, the details of R ⁵³ ~ R ⁵⁵ are as follows.

The blue dye is more preferably a compound represented by 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 C 1-20 saturated hydrocarbon group which may be substituted, a group having an oxygen atom inserted between carbon atoms constituting a C 2-20 alkyl group, and a group which may be substituted Aryl, or aralkyl which may be substituted.

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

In the case where the compound represented by formula (A-II) contains a plurality of cations, the plurality of cations may have the same structure as each other or different structures]

Examples of R ⁵³ , R ⁵⁴ and R ⁵⁷ include the same groups as those exemplified in R ⁴¹ to R ⁴⁴ .

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

Examples of the group represented by R ^{55 in} which an oxygen atom is inserted between carbon atoms constituting the alkyl group include the same groups as those exemplified in R ⁴¹ to R ⁴⁴ . The alkyl group into which an oxygen atom is inserted is preferably a linear alkyl group. In addition, the number of carbons between oxygen atoms is preferably 1 to 4, more preferably 2 to 3.

In R ⁵⁵ , the carbon number of the aryl group is preferably 6-20, more preferably 6-10.

In addition, as the aryl group of R ⁵⁵ , the same groups as those exemplified in R ⁴¹ to R ⁴⁴ may be mentioned, and a phenyl group is preferable.

In the aryl group of R ⁵⁵ , examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and iodine atom; alkoxy groups having 1 to 6 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; sulfamoyl Group; alkylsulfonyl groups with 1 to 6 carbon atoms such as methylsulfonyl; alkoxycarbonyl groups with 2 to 6 carbon atoms such as methoxycarbonyl and ethoxycarbonyl.

In terms of ease of synthesis, R ^{55 is} preferably a saturated hydrocarbon group having 1 to 10 carbon atoms or an aryl group which may be substituted, more preferably an alkyl group having 1 to 8 carbon atoms, or a halogen atom, or 1 carbon atom The alkoxy group of ~4, the hydroxyl group, or the aryl group which may be substituted with a methylsulfonyl group is further preferably a group represented by the following formula. In the following formula, * represents a bond with a carbon atom.

X represents an oxygen atom, -NR ⁵⁷ -or a sulfur atom. Examples of the ring structure including X include groups represented by the following formulas. In the formula, R ⁵³ ~ R ⁵⁵ have the same meanings as 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.

Examples of the cation part of formula (A-I) include cation 1 to cation 27 represented by formula (A-I-1) shown in the following table, and cation 1 to cation 6 and cation 12 are preferred.

In Table 2, Ph1~Ph12 refer to the groups represented by the following formulas.

As the cation in the formula (A-I), cation 1 to cation 6, cation 11, or cation 12 are preferred, and cation 1, cation 2, or cation 12 are particularly preferred.

In the case where the compound represented by formula (A-II) contains a plurality of cations, the plurality of cations may have the same structure as each other or different structures.

The color-curable resin composition of the present invention may contain only one kind of blue dye, or may contain two or more kinds.

The blue dye is preferably a dye soluble in an organic solvent.

染料、萘醌染料、醌亞胺染料、次甲基染料、偶氮次甲基染料、方酸染料、吖啶染料、苯乙烯基染料、香豆素染料、喹啉染料及硝基染料等。 The color-curable resin composition of the present invention may contain dyes other than blue dyes. Examples of dyes other than blue dyes include azo dyes, cyanine dyes,

Dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, azo methine dyes, squaric acid dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes.

The color-setting curable resin composition of the present invention may contain, in addition to a compound containing an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus as an blue atom, and an oxygen atom. Dyes other than blue dyes or blue dyes.

The color-curable resin composition of the present invention may contain a pigment, but preferably contains substantially no pigment. The term "substantially free of pigment" means that the content of the pigment is 0.5% by mass or less, preferably 0% by mass, relative to the blue dye.

As the pigment, well-known pigments can be used, and examples thereof include pigments classified as pigments in the Dye Index (published by The Society of Dyers and Colourists).

Examples of the pigments include blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60; and purple pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, and 38; CI 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; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 , 71, 73 and other orange pigments; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments; CI Pigment Green 7, 36, 58 and other green pigments; CI Pigment Brown 23, 25 and other brown pigments; CI Pigment Black 1, 7 and other black pigments.

By making the pigment contain a pigment dispersant and performing dispersion treatment, a pigment dispersion liquid in which the pigment dispersant is uniformly dispersed in the solution can be prepared. The pigments can be separately dispersed, or a plurality of kinds can be mixed and dispersed.

Examples of the pigment dispersant include pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used alone or in combination of two or more. Examples of pigment dispersants include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie), etc.

The content of the blue dye relative to the total amount of the colorant is usually 1 to 100% by mass, preferably 10 to 100% by mass, more preferably 40 to 100% by mass, and still more preferably 70 to 100% by mass.

Contained as a blue dye, it has a content selected from the group consisting of tungsten, molybdenum, silicon and phosphorus In the case of a dye of at least one element and anion of an oxygen atom in the group, and a dye other than a blue dye or a blue dye, the content of the dye having the anion is preferably 10 relative to the total amount of the blue dye ~100% by mass, more preferably 40-100% by mass, and further preferably 70-100% by mass.

The color-curing resin composition of the present invention may also contain extender pigment (I). Examples of extender pigments include at least one selected from the group consisting of silicon oxide, barium sulfate, titanium oxide, zinc oxide, aluminum oxide, magnesium oxide, and calcium carbonate. In addition, in terms of transparency, the average particle diameter of the extender pigment is preferably 500 nm or less. Among them, in terms of reliability and viscosity, silicon oxide is preferred.

When the body pigment is included, the content of the body pigment (I) is preferably 0.1 to 80 parts by mass, more preferably 1 to 30 parts by mass relative to 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). Copies. If the total amount of extender pigments is within this range, the viscosity and solvent resistance tend to be good.

<Resin (B)>

The resin (B) is preferably an alkali-soluble resin. The alkali-soluble resin is a copolymer containing a structural unit derived from at least one monomer (a) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride.

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

Resin [K1] at least one monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter referred to as "(a)"), and those having 2 to 4 carbon atoms Copolymer of cyclic ether structure and ethylenically unsaturated bond monomer (b) (hereinafter referred to as "(b)"); resin [K2] (a), (b) and (a) Copolymer of monomer (c) copolymerized (where (a) and (b) are different) (hereinafter referred to as "(c)"); copolymerization of resin [K3] (a) and (c) Resin [K4] The resin obtained by reacting the copolymer of (a) and (c) with (b); Resin [K5] a resin obtained by reacting the copolymer of (b) and (c) with (a); resin [K6] reacting the copolymer of (b) and (c) with (a), and then A resin obtained by reacting carboxylic anhydride.

烯-2,3-二羧酸、5-羧基雙環[2.2.1]-2-庚烯、5,6-二羧基雙環[2.2.1]-2-庚烯、5-羧基-5-甲基雙環[2.2.1]-2-庚烯、5-羧基-5-乙基雙環[2.2.1]-2-庚烯、5-羧基-6-甲基雙環[2.2.1]-2-庚烯、5-羧基-6-乙基雙環[2.2.1]-2-庚烯等含有羧基之雙環不飽和化合物類；順丁烯二酸酐、檸康酸酐、伊康酸酐、3-乙烯基鄰苯二甲酸酐、4-乙烯基鄰苯二甲酸酐、3,4,5,6-四氫鄰苯二甲酸酐、1,2,3,6-四氫鄰苯二甲酸酐、二甲基四氫鄰苯二甲酸酐、雙環[2.2.1]-2-庚烯-5,6-二甲酸酐等不飽和二羧酸類酸酐；琥珀酸單[2-(甲基)丙烯醯氧基乙酯]、鄰苯二甲酸單[2-(甲基)丙烯醯氧基乙酯]等2元以上之多元羧酸之不飽和單[(甲基)丙烯醯氧基烷基]酯類；α-(羥基甲基)丙烯酸之類的同一分子中含有羥基及羧基之不飽和丙烯酸酯類等。 Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; maleic acid and fumaric acid , Citraconic acid, methyl fumarate, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, Unsaturated dicarboxylic acids such as 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5-

Ene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]-2-heptene, 5,6-dicarboxybicyclo[2.2.1]-2-heptene, 5-carboxy-5-methyl Bicyclo[2.2.1]-2-heptene, 5-carboxy-5-ethylbicyclo[2.2.1]-2-heptene, 5-carboxy-6-methylbicyclo[2.2.1]-2- Heptene, 5-carboxy-6-ethylbicyclo[2.2.1]-2-heptene and other bicyclic unsaturated compounds containing carboxyl groups; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl Phthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyl Tetrahydrophthalic anhydride, bicyclo[2.2.1]-2-heptene-5,6-dicarboxylic anhydride and other unsaturated dicarboxylic acid anhydrides; succinic acid mono[2-(meth)acryloyloxy Ethyl ester], phthalic acid mono[2-(meth)acryloyloxyethyl] and other unsaturated mono[(meth)acryloyloxyalkyl] esters of polybasic carboxylic acids with at least 2 members; Unsaturated acrylic esters containing hydroxyl and carboxyl groups in the same molecule as α-(hydroxymeth)acrylic acid.

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

(b) For example, it refers to a cyclic ether structure having 2 to 4 carbon atoms (for example, selected from ethylene oxide At least one of the group consisting of a ring, an oxetane ring and a tetrahydrofuran ring) is a polymerizable compound with an ethylenic unsaturated bond.

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

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

Examples of (b) include monomers having an oxirane group and an ethylenically unsaturated bond, monomers having an oxetanyl group and an ethylenically unsaturated bond, and monomers having a tetrahydrofuranyl group and an ethylenically unsaturated bond. The monomer and so on.

As (b), in terms of further improving the reliability of the obtained color filter such as heat resistance and chemical resistance, a monomer having an ethylene oxide group and an ethylenically unsaturated bond is preferred .

酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸炔丙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸苄酯等(甲基)丙烯酸酯類；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯等含羥基之(甲基)丙烯酸酯類； 順丁烯二酸二乙酯、反丁烯二酸二乙酯、伊康酸二乙酯等二羧酸二酯；雙環[2.2.1]-2-庚烯、5-甲基雙環[2.2.1]-2-庚烯、5-乙基雙環[2.2.1]-2-庚烯、5-羥基雙環[2.2.1]-2-庚烯、5-羥基甲基雙環[2.2.1]-2-庚烯、5-(2'-羥基乙基)雙環[2.2.1]-2-庚烯、5-甲氧基雙環[2.2.1]-2-庚烯、5-乙氧基雙環[2.2.1]-2-庚烯、5,6-二羥基雙環[2.2.1]-2-庚烯、5,6-二(羥基甲基)雙環[2.2.1]-2-庚烯、5,6-二(2'-羥基乙基)雙環[2.2.1]-2-庚烯、5,6-二甲氧基雙環[2.2.1]-2-庚烯、5,6-二乙氧基雙環[2.2.1]-2-庚烯、5-羥基-5-甲基雙環[2.2.1]-2-庚烯、5-羥基-5-乙基雙環[2.2.1]-2-庚烯、5-羥基甲基-5-甲基雙環[2.2.1]-2-庚烯、5-第三丁氧基羰基雙環[2.2.1]-2-庚烯、5-環己氧基羰基雙環[2.2.1]-2-庚烯、5-苯氧基羰基雙環[2.2.1]-2-庚烯、5,6-雙(第三丁氧基羰基)雙環[2.2.1]-2-庚烯、5,6-雙(環己氧基羰基)雙環[2.2.1]-2-庚烯等雙環不飽和化合物類；N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苄基順丁烯二醯亞胺、N-丁二醯亞胺基-3-順丁烯二醯亞胺苯甲酸酯、N-丁二醯亞胺基-4-順丁烯二醯亞胺丁酸酯、N-丁二醯亞胺基-6-順丁烯二醯亞胺己酸酯、N-丁二醯亞胺基-3-順丁烯二醯亞胺丙酸酯、N-(9-吖啶基)順丁烯二醯亞胺等二羰基醯亞胺衍生物類；苯乙烯、α-甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、乙烯基甲苯、對甲氧基苯乙烯、丙烯腈、甲基丙烯腈、氯乙烯、偏二氯乙烯、丙烯醯胺、甲基丙烯醯胺、乙酸乙烯酯、1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯等。 Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and (meth)acrylic acid. Tributyl ester, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid ring Amyl ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]-8-decyl ester (meth) In the field, it is called "dicyclopentyl (meth)acrylate" as a common name. There are also cases called "tricyclodecyl (meth)acrylate"), tricyclo (meth)acrylate [ 5.2.1.0 ^2,6 ]-8-decenyl ester (in this technical field, it is called "dicyclopentenyl (meth)acrylate" as a common name), dicyclopentanyl (meth)acrylate Oxyethyl ester, (meth)acrylic acid

Ester, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, (meth)acrylic acid (Meth)acrylates such as benzyl ester; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and other hydroxyl-containing (meth)acrylates; maleic acid diacid Dicarboxylic acid diesters such as ethyl ester, diethyl fumarate, and diethyl iconate; bicyclo[2.2.1]-2-heptene, 5-methylbicyclo[2.2.1]-2- Heptene, 5-ethylbicyclo[2.2.1]-2-heptene, 5-hydroxybicyclo[2.2.1]-2-heptene, 5-hydroxymethylbicyclo[2.2.1]-2-heptene , 5-(2'-hydroxyethyl) bicyclo[2.2.1]-2-heptene, 5-methoxybicyclo[2.2.1]-2-heptene, 5-ethoxybicyclo[2.2.1 ]-2-heptene, 5,6-dihydroxybicyclo[2.2.1]-2-heptene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]-2-heptene, 5,6 -Bis(2'-hydroxyethyl)bicyclo[2.2.1]-2-heptene, 5,6-dimethoxybicyclo[2.2.1]-2-heptene, 5,6-diethoxy Bicyclo[2.2.1]-2-heptene, 5-hydroxy-5-methylbicyclo[2.2.1]-2-heptene, 5-hydroxy-5-ethylbicyclo[2.2.1]-2-heptane Ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]-2-heptene, 5-t-butoxycarbonylbicyclo[2.2.1]-2-heptene, 5-cyclohexyloxy Carbonyl bicyclo[2.2.1]-2-heptene, 5-phenoxycarbonyl bicyclo[2.2.1]-2-heptene, 5,6-bis(third butoxycarbonyl)bicyclo[2.2.1] -2-heptene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]-2-heptene and other bicyclic unsaturated compounds; N-phenyl maleimide diimide, N- Cyclohexyl maleimide diimide, N-benzyl maleimide diimide, N-butylimide-3-maleimide benzoate, N-butane diimide Imino-4-maleimide butyralimidate, N-butadiene imido-6-maleimide hexanoate, N-butadiene imido-3- Dicarbonylimide derivatives such as maleimide propionate, N-(9-acridinyl)maleimide diimide; styrene, α-methylstyrene, m-methyl Styrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, propylene amide, methacryl amide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

Among these, in terms of copolymerization reactivity and heat resistance, styrene, vinyltoluene, benzyl (meth)acrylate, (meth)acrylic acid tricyclo[5.2.1.0 ^2,6 ]-8-decyl ester, N-phenyl maleimide diimide, N-cyclohexyl maleimide diimide, N-benzyl maleimide diimide, bicyclic [2.2.1 ]-2-heptene.

Specific examples of the resin (B) include: (meth)acrylic acid 3,4-epoxycyclohexyl methyl ester/(meth)acrylic acid copolymer, (meth)acrylic acid 3,4-epoxy tricyclic [5.2.1.0 ^2.6 ] Resin such as decyl ester/(meth)acrylic acid copolymer [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, (meth ) Glycidyl acrylate/styrene/(meth)acrylic acid copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2.6 ]decyl ester/(meth)acrylic acid/N-cyclohexyl cis Butylenediimide copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2.6 ]decyl ester/(meth)acrylic acid/vinyltoluene copolymer, 3-methyl-3- (Meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer and other resins [K2]; (meth)acrylic acid benzyl ester/(meth)acrylic acid copolymer, styrene /(Meth)acrylic copolymer, benzyl (meth)acrylate/tricyclodecyl (meth)acrylate/(meth)acrylic copolymer and other resins [K3]; in benzyl (meth)acrylate/( A resin obtained by adding glycidyl (meth)acrylate to a meth)acrylic copolymer, and adding (meth) to a tricyclodecyl (meth)acrylate/styrene/(meth)acrylic copolymer Glycidyl acrylate resin, resin obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer Etc. resin [K4]; resin obtained by reacting copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid, tricyclodecyl (meth)acrylate /Styrene/(meth)acrylic acid copolymer of glycidyl ester and (meth)acrylic acid resin and other resins [K5]; trimethydecyl (meth)acrylate/glycidyl (meth)acrylate The resin obtained by reacting the ester copolymer with (meth)acrylic acid and the resin obtained by reacting with tetrahydrophthalic anhydride [K6], etc.

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

For example, the resin [K1] can be used for example in the document "Experimental Method of Polymer Synthesis" (by Otsu Takayuki, Publisher: Chemical Dojin Co., Ltd., first edition, first print, 1972) The method described in March 1st) and the cited documents described in this document are manufactured as references.

The weight average molecular weight in terms of polystyrene of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. If the molecular weight is within the above range, the hardness of the coating film will increase, the residual film rate will also be high, the solubility in the developer of the unexposed portion will be good, and the resolution of the colored pattern will tend to increase.

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

The acid value of the resin (B) is preferably 30 to 170 mg-KOH/g, more preferably 40 to 150 mg-KOH/g, and still more preferably 50 to 135 mg-KOH/g. Here, the acid value is a value measured in terms of the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and it can be obtained by titration using a potassium hydroxide aqueous solution, for example.

The content of the resin (B) relative to the total amount of solid content is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass. Here, the "total amount of solid content" in this specification refers to the amount obtained by removing the content of the solvent from the total amount of the colored curable resin composition. The total amount of solid components and the content of each component relative thereto can be measured by a known analysis method such as liquid chromatography or gas chromatography.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized due to active radicals and/or acids generated by the polymerization initiator (D), and examples include compounds having a polymerizable ethylenic unsaturated bond, etc., preferably It is a (meth)acrylate compound.

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

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

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

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

The content of the polymerizable compound (C) relative to the total amount of solid content is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass.

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

If the content of the polymerizable compound (C) is within the above range, the residual film rate during the formation of the colored pattern and the chemical resistance of the color filter tend to increase.

<polymerization initiator (D)>

化合物、醯基氧化膦化合物、O-醯基肟化合物及聯咪唑化合物。 The polymerization initiator (D) is not particularly limited as long as it can generate active radicals, acids, etc. by the action of light or heat and starts polymerization, and a known polymerization initiator can be used. Examples of polymerization initiators that generate active radicals include alkyl ketone compounds and

Compounds, acyl phosphine oxide compounds, O-acyl oxime compounds and biimidazole compounds.

Examples of the O-acyl oxime compounds include N-benzyloxy-1-(4-phenylthiophenyl)-1-butanone-2-imine and N-benzyloxy -1-(4-phenylthiophenyl)-1-octanone-2-imine, N-benzyloxy-1-(4-phenylthiophenyl)-3-cyclopentyl-1 -Acetone-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]ethane-1- Imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolylmethoxy ) Benzoamide}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzylamide )-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl amide Group)-9H-carbazol-3-yl]-3-cyclopentyl-1-acetone-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (made by BASF) and N-1919 (made by ADEKA) can also be used. Among them, the O-acyl oxime compound is preferably selected from N-benzyloxy-1-(4-phenylthiophenyl)-1-butanone-2-imine, N-benzyloxy -1-(4-phenylthiophenyl)-1-octanone-2-imine and N-benzyloxy-1-(4-phenylthiophenyl)-3-cyclopentyl-1 -At least one of the groups consisting of acetone-2-imine, more preferably N-benzyloxy-1-(4-phenylthiophenyl)-1-octanone-2-imine. In the case of these O-acyl oxime compounds, there is a tendency to obtain high-brightness color filters.

啉基-1-(4-甲基巰基苯基)-1-丙酮、2-二甲基胺基-1-(4-

啉基苯基)-2-苄基-1-丁酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-

啉基)苯基]-1-丁酮、2-羥基-2-甲基-1-苯基-1-丙酮、2-羥基-2-甲基-1-[4-(2-羥基乙氧基)苯基]-1-丙酮、1-羥基環己基苯基酮、2-羥基-2-甲基-1-(4-異丙烯基苯基)-1-丙酮之低聚物、α,α-二乙氧基苯乙酮、苯偶醯二甲基縮酮 等。亦可使用Irgacure369、907、379(以上為BASF公司製造)等市售品。 Examples of the alkyl benzophenone compounds include 2-methyl-2-

Plinyl-1-(4-methylmercaptophenyl)-1-acetone, 2-dimethylamino-1-(4-

Phenylphenyl)-2-benzyl-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-

Phenyl)phenyl)-1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy Yl)phenyl]-1-acetone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)-1-acetone oligomer, α, α-diethoxyacetophenone, benzoyl dimethyl ketal, etc. Commercial products such as Irgacure 369, 907, and 379 (above are manufactured by BASF Corporation) can also be used.

化合物，例如可列舉：2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三

、2,4-雙(三氯甲基)-6-向日葵基-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三

等。 As the above three

Compounds, for example: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tris

, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-sunflower group-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tris

, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-tri

Wait.

Examples of the above-mentioned acylphosphine oxide compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide and the like. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF) can also be used.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3 -Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, 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'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5' -Tetrakis(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2, 2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Laid-Open No. 48-38403, Japanese Patent Laid-Open JP 62-174204, etc.), imidazole compounds in which the phenyl group at 4,4', 5,5'-position is substituted with carboalkoxy (for example, refer to Japanese Patent Laid-Open No. 7-10913, etc.).

Furthermore, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl phthaloyl benzoate , 4-phenylbenzophenone, 4-benzyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis (third butyl peroxycarbonyl) diphenyl Ketone, 2,4,6-tri Benzophenone compounds such as methylbenzophenone; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinone compounds; 10-butyl-2-chloroacridone, benzophenone, benzene Methyl glyoxylate, titanocene compounds, etc. These are preferably used in combination with the following polymerization initiation aid (D1) (especially amines).

Examples of the acid generator include 4-hydroxyphenyl dimethyl benzoic acid p-toluenesulfonate, 4-hydroxyphenyl dimethyl benzoic acid hexafluoroantimonate, and 4-acetoxyphenyl dimethyl A-toluenesulfonate, 4-acetoxyphenyl-methyl-benzylammonium hexafluoroantimonate, triphenylammonium p-toluenesulfonate, triphenylammonium hexafluoroantimonate, diphenyl Onium salts such as p-toluenesulfonate, diphenylphosphonium hexafluoroantimonate, or nitrobenzyl tosylate, benzoin tosylate, etc.

化合物、醯基氧化膦化合物、O-醯基肟化合物及聯咪唑化合物所組成之群中之至少一種之聚合起始劑，更佳為包含O-醯基肟化合物之聚合起始劑。 As the polymerization initiator (D), it is preferable to contain

The polymerization initiator of at least one of the group consisting of a compound, an acyl phosphine oxide compound, an O-acyl oxime compound and a biimidazole compound is more preferably a polymerization initiator containing an O-acyl oxime compound.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more 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). If the content of the polymerization initiator (D) is within the above range, the exposure time tends to be shortened due to high sensitivity, so the productivity of the color filter is improved.

<Polymerization Initiator (D1)>

The polymerization start aid (D1) is a compound or sensitizer for promoting the polymerization of the polymerizable compound that starts polymerization by the polymerization initiator. When the polymerization start aid (D1) is included, it can usually be used in combination with the polymerization starter (D).

化合物及羧酸化合物等。 Examples of the polymerization start aid (D1) include amine compounds, alkoxyanthracene compounds, and 9-oxosulfur

Compounds and carboxylic acid compounds.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-diethylaminobenzoate Isoamyl methylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl p-toluidine, 4 ,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethyl Methylmethylamino) benzophenone and the like, among which 4,4'-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (Hodogaya Chemical Industry Co., Ltd.) can also be used.

Examples of the alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl -9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

化合物，可列舉：2-異丙基9-氧硫

、4-異丙基9-氧硫

、2,4-二乙基9-氧硫

、2,4-二氯9-氧硫

、1-氯-4-丙氧基9-氧硫

等。 As the above 9-oxygen sulfur

Compounds include: 2-isopropyl 9-oxysulfur

, 4-isopropyl 9-oxysulfur

, 2,4-Diethyl 9-oxysulfur

, 2,4-Dichloro 9-oxysulfur

, 1-chloro-4-propoxy 9-oxysulfur

Wait.

Examples of the above-mentioned carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, and methoxyphenylthio Acetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine , Naphthoxyacetic acid, etc.

In the case of using these polymerization initiation aids (D1), the content is 100 parts by mass relative to the total amount of the resin (B) and the polymerizable compound (C), preferably 0.1 to 30 parts by mass, more preferably 1~20 parts by mass. If the amount of the polymerization initiation aid (D1) is within this range, the coloring pattern can be further formed with high sensitivity, and the productivity of the color filter tends to be improved.

<silsesquioxane compound (H)>

The silsesquioxane compound (H) refers to a compound represented by formula (1) whose main chain skeleton contains Si-O bonds.

[(RSiO _3/2 ) _n ] (1)

(In the formula, R represents an organic group, n represents a natural number)

R represents a monovalent organic group. As the monovalent organic group, a monovalent hydrocarbon which may be substituted may be mentioned base.

Examples of the hydrocarbon group include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, second butyl group and third butyl group , Pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl and other aliphatic hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 carbon atom ~12 alkyl.

Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as phenyl, naphthyl, benzyl, tolyl, and styryl groups.

Examples of the substituent which may have a monovalent hydrocarbon group include (meth)acryloyl groups, hydroxyl groups, mercapto groups, carboxyl groups, isocyanate groups, amine groups, and urea groups. In addition, -CH ₂ -contained in the monovalent hydrocarbon group may be substituted with -O-, -S-, carbonyl, or the like.

The monovalent organic group represented by R preferably contains at least one reactive group. The so-called reactive group refers to a group that can react with other parts by chemical reaction.

Examples of the reactive group include vinyl, allyl, (meth)acryloyl, styryl, oxirane, oxetanyl, carboxyl, hydroxy, thiocyclopropyl, and mercapto. , Isocyanate group, amine group and urea group, preferably (meth)acryloyl group, mercapto group and ethylene oxide group.

The silsesquioxane compound (H) can be exemplified by a cage type, a ladder type or a random type, preferably a random type.

The cage type silsesquioxane compound may be a complete cage type or an incomplete cage type silsesquioxane compound such as a part of the cage being opened.

Examples of the silsesquioxane compound (H) include: silsesquioxane described in Japanese Patent Laid-Open No. 2011-128239, AC-SQ TA-100, MAC-SQ TM-100, AC-SQ SI-20, MAC-SQ SI-20, MAC-SQ HDM, OX-SQ TX-100, OX-SQ SI-20, OX-SQ ME-20, OX-SQ HDX (manufactured by East Asia Synthetic Co., Ltd.), Compoceran (registered trademark) SQ107, Compoceran (registered trademark) Standard) SQ109, Compoceran (registered trademark) SQ506, Compoceran (registered trademark) SQ502-6 (Arakawa Chemical Industry Co., Ltd.), etc.

The color-curing resin composition of the present invention may also contain two or more silsesquioxane compounds (H).

The silsesquioxane compound (H) is preferably insoluble in an alkaline aqueous solution.

The content of the silsesquioxane compound (H) is usually 5 to 3000 parts by mass, preferably 15 to 3000 parts by mass, more preferably 25 to 3000 parts by mass, and more preferably 100 parts by mass of the blue dye. 35~2500 parts by mass, especially 60~2000 parts by mass. The higher the content of silsesquioxane relative to the blue dye, the more significant the effect of improving chemical resistance becomes.

<thiol compound (T)>

The thiol compound (T) is a compound having a mercapto group in the molecule.

-2,4,6(1H,3H,5H)-三酮、1,3,5-三(3-巰基丁氧基乙基)-1,3,5-三

-2,4,6(1H,3H,5H)-三酮等。 Specific examples of the thiol compound (T) include, for example, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol dithiopropionate, butanediol disulfide Glycolate, ethylene glycol dithioglycolate, trimethylolpropane trithioglycolate, butanediol dithiopropionate, trimethylolpropane trithiopropionate, three Hydroxymethylpropane trithioglycolate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioglycolate, trihydroxyethyl trithiopropionate, pentaerythritol tetra(3-mercaptobutyrate), 1 ,4-bis(3-mercaptobutaneoxy)butane, dipentaerythritol hexathiopropionate, dipentaerythritol hexa(3-mercaptobutyrate), 1,3,5-trimercaptopropionate-1 ,3,5-three

-2,4,6(1H,3H,5H)-trione, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-tris

-2,4,6(1H,3H,5H)-trione etc.

The content of the thiol compound (T) in the color-curing resin composition of the present invention is calculated as a mass fraction relative to the total amount of the polymerization initiator (D), preferably 2 to 70% by mass, more preferably 5 to 50% by mass. If the content of the thiol compound (T) is within the above range, the sensitivity is increased and the developability tends to be good, which is preferable.

<Solvent (E)>

Examples of the solvent (E) include ester solvents (solvents containing -COO- in the molecule and not containing -O-), Ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (containing -CO- in the molecule and not containing- COO-solvent), alcohol solvent (solvent that contains OH in the molecule and does not contain -O-, -CO- and -COO-), aromatic hydrocarbon solvent, amide solvent, dimethyl sulfoxide, etc.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, 2-hydroxyisobutyric acid methyl ester, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. , Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclic Hexanol acetate, propylene glycol diacetate, ethylene glycol diacetate, γ-butyrolactone, etc.

烷、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇甲基乙醚、二乙二醇二丙醚、二乙二醇二丁醚、苯甲醚、苯乙醚、甲基苯甲醚等。 Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monoethyl ether. Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, Tetrahydrofuran, tetrahydropyran, 1,4-di

Alkanes, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether, methyl Anisole etc.

Examples of ether ester solvents include: methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl acetate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethoxy-2-methylpropionic acid ethyl ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether ethyl Ester, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate , Dipropylene glycol methyl ether acetate, etc.

Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2- Heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, isophorone, etc.

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

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

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

The solvent (E) is preferably an ester solvent, ether solvent, ether ester solvent or ketone solvent, more preferably propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, Ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol or 4-hydroxy-4-methyl-2-pentanone, further preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-Methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate or 4-hydroxy-4-methyl-2-pentanone.

The solvent (E) may be used alone or in combination of two or more.

When two or more solvents are used in combination, the color-curable resin composition of the present invention preferably contains at least one selected from the group consisting of ether ester solvents and ketone solvents, and more preferably contains ether ester solvents and ketones. Both of solvents.

The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass relative 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, and more preferably 8 to 25% by mass. If the content of the solvent (E) is within the above range, the flatness during coating becomes good, and since the color density is not insufficient when forming the color filter, the display characteristics tend to be good.

<Leveling agent (F)>

Examples of the leveling agent (F) include polysiloxane-based surfactants and fluorine-based surfactants Agents and polysiloxane-based surfactants with fluorine atoms. These may have a polymerizable group in the side chain.

Examples of polysiloxane-based surfactants include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, the same series SH7PA, the same series DC11PA, the same series SH21PA, the same series SH28PA, the same series SH29PA, the same series SH30PA, the same series SH8400 (trade name: manufactured by Dow Corning Toray Co., Ltd.) , KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan LLC) )Wait.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specific examples include Fluorad (registered trademark) FC430, the same series FC431 (made by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, the same series F171, the same series F172, the same series F173, the same series F177, the same Series F183, same series F554, same series R30, same series RS-718-K (made by DIC Corporation), Eftop (registered trademark) EF301, same series EF303, same series EF351, same series EF352 (Mitsubishi Materials Electronic Chemicals shares Co., Ltd.), Surflon (registered trademark) S381, the same series S382, the same series SC101, the same series SC105 (made by Asahi Glass Co., Ltd.) and E5844 (made by Daikin Precision Chemical Research Institute Co., Ltd.), etc.

Examples of the polysiloxane-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, MEGAFAC (registered trademark) R08, the same series BL20, the same series F475, the same series F477, and the same F443 (manufactured by DIC Co., Ltd.) and the like can be mentioned.

Regarding the content of the leveling agent (F), with respect to the total amount of the colored curable resin composition, It is preferably 0.001 mass% or more and 0.2 mass% or less, preferably 0.002 mass% or more and 0.1 mass% or less, more preferably 0.01 mass% or more and 0.05 mass% or less. Furthermore, this content does not include the content of the pigment dispersant. If the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Antioxidant (G)>

Examples of the antioxidant (G) include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants and sulfur-based antioxidants, preferably phenol-based antioxidants and phosphorus-based antioxidants.

The phenolic antioxidant is an antioxidant having a phenolic hydroxyl group in the molecule, and preferably has a branched alkyl group adjacent to the -OH group of the phenolic hydroxyl group. In this specification, all antioxidants having a phenolic hydroxyl group and a phosphate structure or a phosphite structure are classified as phosphorus-based antioxidants.

-2,4,6(1H,3H,5H)-三酮、1,3,5-三((4-第三丁基-3-羥基-2,6-二甲苯基)甲基)-1,3,5-三

-2,4,6(1H,3H,5H)-三酮、硫代二伸乙基雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]、苯丙酸-3,5-雙(1,1-二甲基乙基)-4-羥基-C7-C9側鏈烷基酯、4,6-雙(辛基硫代甲基)-鄰甲酚、Irganox(註冊商標)3125(BASF公司製造)、2,4-雙(正辛基硫代)-6-(4-羥基3',5'-二第三丁基苯胺基)-1,3,5-三

、3,9-雙(2-(3-(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧基)-1,1-二甲基乙基)-2,4,8,10-四氧雜螺(5,5)十一烷、 Sumilizer(註冊商標)BHT(住友化學股份有限公司製造)、Sumilizer(註冊商標)GA-80(住友化學股份有限公司製造)、Sumilizer(註冊商標)GS(住友化學股份有限公司製造)、Cyanox(註冊商標)1790(Cytec股份有限公司製造)及維生素E(Eisai股份有限公司製造)等。 Examples of phenolic antioxidants include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane and 4,4'-butylene-bis(3 -Methyl-6-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, acrylic acid 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl ester, (tetrakis[methylene-3-(3,5- Di-tert-butyl-4-hydroxyphenyl) propionate] methane, pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3-(3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, 3,3',3",5,5',5"-hexa-tert-butyl-a,a', a"-(mesitylene-2,4,6-triyl)tri-p-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1, 3,5-three

-2,4,6(1H,3H,5H)-trione, 1,3,5-tris((4-tert-butyl-3-hydroxy-2,6-xylyl)methyl)-1 ,3,5-three

-2,4,6(1H,3H,5H)-trione, thiodiethylidene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], benzene Propionic acid-3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 side chain alkyl ester, 4,6-bis(octylthiomethyl)-o-cresol , Irganox (registered trademark) 3125 (manufactured by BASF), 2,4-bis(n-octylthio)-6-(4-hydroxy3',5'-di-tert-butylanilinyl)-1,3 ,5-three

, 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2, 4,8,10-Tetraoxa spiro (5,5) undecane, Sumilizer (registered trademark) BHT (made by Sumitomo Chemical Co., Ltd.), Sumilizer (registered trademark) GA-80 (made by Sumitomo Chemical Co., Ltd.) , Sumilizer (registered trademark) GS (made by Sumitomo Chemical Co., Ltd.), Cyanox (registered trademark) 1790 (made by Cytec Co., Ltd.), and vitamin E (made by Eisai Co., Ltd.), etc.

The so-called amine antioxidant is an antioxidant having an amine group in the molecule.

、N-甲基酚噻

、N-乙基酚噻

、3,7-二辛基酚噻

、酚噻

羧酸酯、酚硒

等酚噻

系抗氧化劑。 Examples of the amine antioxidant include 1-naphthylamine, phenyl-1-naphthylamine, p-octylphenyl-1-naphthylamine, p-nonylphenyl-1-naphthylamine, p Naphthylamine-based antioxidants such as dodecylphenyl-1-naphthylamine, phenyl-2-naphthylamine; N,N'-diisopropyl-p-phenylenediamine, N,N'-di Isobutyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di-β-naphthyl-p-phenylenediamine, N-phenyl-N'-isopropyl -P-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine, dioctyl- Phenylenediamine, phenylhexyl-p-phenylenediamine, phenyloctyl-p-phenylenediamine and other phenylenediamine-based antioxidants; dipyridylamine, diphenylamine, p, p-di-n-butyl Diphenylamine, p, p'-di-third butyl diphenylamine, p, p'-di-third pentyl diphenylamine, p, p'-dioctyldiphenylamine, p , P-dinonyldiphenylamine, p, p-didecyldiphenylamine, p, p-di-dodecyldiphenylamine, p, p-stilbene Diphenylamine, p, p-dimethoxydiphenylamine, 4,4'-bis(4-α,α-dimethylbenzyl)diphenylamine, p-isopropoxy Diphenylamine-based antioxidants such as diphenylamine and dipyridylamine; phenol thiophene

N-methylphenol

N-ethylphenol

, 3,7-dioctylphenolthio

Phenothiazine

Carboxylate, phenol selenium

Isophenol

Department of antioxidants.

The phosphorus-based antioxidant is an antioxidant having a phosphate structure or a phosphite structure.

磷環庚烷、三(2,4-二第三丁基苯基)亞磷酸酯、二苯基異辛基亞磷酸酯、2,2'-亞甲基雙(4,6-二第三丁基苯基)辛基亞磷酸酯、二苯基異癸基亞磷酸酯、二苯基異癸基亞磷酸酯、磷酸三苯酯、磷酸三丁酯、二硬脂 基季戊四醇二亞磷酸酯、環狀新戊烷四基雙(2,6-二第三丁基-4-甲基苯基)亞磷酸酯、6-[3-(3-第三丁基-4-羥基-5-甲基苯基)丙氧基]-2,4,8,10-四-第三丁基苯并[d,f][1,3,2]二

磷環庚烷、三(壬基苯基)亞磷酸酯、三(混合單-&二壬基苯基)亞磷酸酯、二苯基單(十三烷基)亞磷酸酯、2,2'-亞乙基雙(4,6-二第三丁基苯酚)氟亞磷酸酯、苯基二異癸基亞磷酸酯、三(2-乙基己基)亞磷酸酯、三(異癸基)亞磷酸酯、三(十三烷基)亞磷酸酯、四(2,4-二第三丁基苯基)-4,4'-伸聯苯基-二亞膦酸二酯、4,4'-異亞丙基二苯基四烷基(C12-C15)二亞磷酸酯、4,4'-亞丁基雙(3-甲基-6-第三丁基苯基)-二(十三烷基)亞磷酸酯、雙(壬基苯基)季戊四醇二亞磷酸酯、雙(2,4-二第三丁基苯基)季戊四醇-二亞磷酸酯、環新戊烷四基雙(2,6-二第三丁基-4-甲基苯基-亞磷酸酯)、1,1,3-三(2-甲基-4-二(十三烷基)亞磷酸酯基-5-第三丁基苯基)丁烷、四(2,4-二第三丁基-5-甲基苯基)-4,4'-伸聯苯基二亞膦酸二酯、三-2-乙基己基亞磷酸酯、三異癸基亞磷酸酯、三硬脂基亞磷酸酯、苯基二異癸基亞磷酸酯、三月桂基三硫代亞磷酸酯、二硬脂基季戊四醇二亞磷酸酯、三(壬基苯基)亞磷酸酯三[2-[[2,4,8,10-四-第三丁基二苯并[d,f][1,3,2]二氧雜膦-6-基]氧基]乙基]胺、亞磷酸雙(2,4-雙(1,1-二甲基乙基)-6-甲基苯基)乙酯、Adeka stab(註冊商標)329K(ADEKA股份有限公司製造)、Adeka stab(註冊商標)PEP36(ADEKA股份有限公司製造)、Adeka stab(註冊商標)PEP-8(ADEKA股份有限公司製造)、Sandstab(註冊商標)P-EPQ(Clariant公司製造)、Weston(註冊商標)618(GE公司製造)、Weston(註冊商標)619G(GE公司製造)、Ultranox(註冊商標)626(GE公司製造)、6-[3-(3-第三丁基-4-羥基-5-甲基苯基)丙氧基]-2,4,8,10-四-第三丁基二苯并[d,f][1,3,2]二

磷環庚烷等。 Examples of phosphorus-based antioxidants include: 6-[3-(3-tertiarybutyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra- Tributyldibenzo[d,f][1,3,2]di

Phosphocycloheptane, tris(2,4-di-tert-butylphenyl) phosphite, diphenyl isooctyl phosphite, 2,2'-methylene bis(4,6-di-third Butylphenyl) octyl phosphite, diphenyl isodecyl phosphite, diphenyl isodecyl phosphite, triphenyl phosphate, tributyl phosphate, distearyl pentaerythritol diphosphite , Cyclic neopentane tetrayl bis (2,6-di-t-butyl-4-methylphenyl) phosphite, 6-[3-(3-tert-butyl-4-hydroxy-5- Methylphenyl)propoxy]-2,4,8,10-tetra-tert-butylbenzo[d,f][1,3,2]di

Phosphocycloheptane, tri(nonylphenyl) phosphite, tri(mixed mono-& dinonylphenyl) phosphite, diphenyl mono(tridecyl) phosphite, 2,2' -Ethylene bis(4,6-di-tert-butylphenol) fluorophosphite, phenyl diisodecyl phosphite, tri(2-ethylhexyl) phosphite, tri(isodecyl) Phosphite, tris(tridecyl)phosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene-diphosphinic acid diester, 4,4 '-Isopropylidene diphenyltetraalkyl (C12-C15) diphosphite, 4,4'-butylene bis(3-methyl-6-third butylphenyl)-di(thirteen Alkyl) phosphite, bis(nonylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol-diphosphite, cycloneopentane tetrayl bis(2 ,6-ditributyl-4-methylphenyl-phosphite), 1,1,3-tris(2-methyl-4-bis(tridecyl)phosphite-5- Tert-butylphenyl)butane, tetrakis(2,4-di-tert-butyl-5-methylphenyl)-4,4'-biphenylene diphosphinite diester, tri-2- Ethylhexyl phosphite, triisodecyl phosphite, tristearyl phosphite, phenyl diisodecyl phosphite, trilauryl trithiophosphite, distearyl pentaerythritol disulfite Phosphate, tri(nonylphenyl) phosphite tri[2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]diox Heterophosphine-6-yl]oxy]ethyl]amine, bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl phosphite, Adeka stab (registered Trademark) 329K (made by ADEKA Corporation), Adeka stab (registered trademark) PEP36 (made by ADEKA Corporation), Adeka stab (registered trademark) PEP-8 (made by ADEKA Corporation), Sandstab (registered trademark) P- EPQ (manufactured by Clariant), Weston (registered trademark) 618 (manufactured by GE), Weston (registered trademark) 619G (manufactured by GE), Ultranox (registered trademark) 626 (manufactured by GE), 6-[3-(3 -Tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2 ]two

Phosphorocycloheptane, etc.

The so-called sulfur-based antioxidant is an antioxidant having a sulfur atom in the molecule.

Examples of sulfur-based antioxidants include dilauryl thiodipropionate and dime Β-alkylmercaptopropionic acid of dialkyl thiodipropionate compounds such as myristyl ester or distearyl ester and tetra[methylene(3-dodecylthio)propionate]methane and other polyols Ester compounds, etc.

The color-curable resin composition of the present invention may contain two or more antioxidants.

The content of the antioxidant (G) in the present invention is usually 0.1 to 10% by mass, preferably 0.5 to 8% by mass, and more preferably 1 to 6% by mass relative to the total amount of solid content. Within the above-mentioned range, it is preferably dispersed in the colored curable resin composition without any precipitation of components, which is less likely to affect the color characteristics of the obtained color filter.

<other ingredients>

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

<Manufacturing method of colored curable resin composition>

The color-curable resin composition of the present invention can be obtained, for example, by combining blue dye (A), resin (B), polymerizable compound (C), polymerization initiator (D), silsesquioxane compound (H) , And the solvent (E), leveling agent (F), antioxidant (G), polymerization initiation aid (D1), thiol compound (T), pigment, and other components that can be used as required to prepare.

When a pigment is included, the pigment is preferably mixed with part or all of the solvent (E) in advance, and dispersed using a bead mill or the like until the average particle diameter of the pigment reaches about 0.2 μm or less. At this time, part or all of the above pigment dispersant and resin (B) may be blended as needed. The target colored curable resin composition can be prepared by mixing the remaining components in the pigment dispersion obtained in the above-described manner so as to have a specific concentration.

The dye may be dissolved in part or all of the solvent (E) to prepare a solution in advance, or may be dispersed in part or all of the solvent (E) to prepare a dye dispersion in advance. When preparing a dye dispersion liquid, a dispersant used in the art can also be used. Preferably using holes A filter with a diameter of about 0.01 to 1 μm filters the solution.

Preferably, the color-curing resin composition after mixing is filtered using a filter with a pore diameter of about 0.01 to 10 μm.

<Manufacturing method of color filter>

Examples of the method for producing a colored pattern from the color-curable resin composition of the present invention include photolithography, inkjet method, and printing method. Among them, the photolithography method is preferred. The photolithography method is a method of applying the above-mentioned colored curable resin composition to a substrate, drying it to form a coloring composition layer, and exposing the colored composition layer through a photomask for development. In the photolithography method, by not using a photomask during exposure and/or not performing development, a colored coating film that is a cured product of the coloring composition layer can be formed. The color pattern or colored coating film thus formed is the color filter of the present invention.

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

As the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass coated with silica on the surface, or polycarbonate, polymethyl methacrylate, and polyparaphenylene can be used Resin plates such as ethylene dicarboxylate, silicon, and aluminum, silver, silver/copper/palladium alloy thin films, etc. formed on the substrate. Other color filter layers, resin layers, transistors, circuits, etc. can also be formed on these substrates.

The formation of pixels of various colors by photolithography can be performed by a known or conventional device or condition. For example, it can be produced by the following method.

First, the colored curable resin composition is applied to the substrate, and then heated and dried (pre-baked) and/or dried under reduced pressure, thereby removing and drying the volatile components such as the solvent to obtain a smooth colored composition Floor.

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

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

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

The film thickness of the coloring composition layer is not particularly limited, as long as it is appropriately selected according to the film thickness of the target color filter.

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

As a light source used for exposure, a light source with a wavelength of 250 to 450 nm is preferred. For example, a filter that cuts off this wavelength region can be used to cut off light that does not reach 350 nm, or a bandpass filter that extracts these wavelength regions can be used to selectively extract light near 436 nm, around 408 nm, or around 365 nm. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

In order to uniformly irradiate parallel light to the entire exposure surface, or to align the exact position of the mask and the substrate on which the colored composition layer is formed, it is preferable to use a mask to align the exposure device such as an exposure machine and a stepper.

The exposed coloring composition layer is brought into contact with a developing solution for development, thereby forming a coloring pattern on the substrate. By development, the unexposed portion of the coloring composition layer is dissolved in the developer and removed. As the developing solution, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide is preferable. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Furthermore, the developer may contain a surfactant.

The developing method may be any of a paddle method, a dipping method, and a spray method. Furthermore, the substrate may be inclined at an arbitrary angle during development.

After development, it is preferably washed with water.

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

According to the color-curing resin composition of the present invention, a color filter with particularly excellent brightness can be produced. This color filter is more useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL (Electroluminescence) devices, electronic paper, etc.) and solid-state imaging devices. Among them, it is more useful as a color filter for a liquid crystal display device.

[Example]

Hereinafter, the color-curable resin composition of the present invention will be described in more detail by examples. Unless otherwise specified, "%" and "parts" in the examples refer to mass% and mass parts.

In the following synthesis examples, the compounds were identified by mass analysis (LC: Model 1200 manufactured by Agilent, MASS: LC/MSD model manufactured by Agilent) or elemental analysis (VARIO-EL manufactured by Elementar Corporation).

[Synthesis Example 1]

The following reaction is carried out under a nitrogen atmosphere. After adding 36.3 parts of potassium thiocyanate and 160 parts of acetone to the flask equipped with a condenser and a stirring device, it stirred at room temperature for 30 minutes. Then, 50 parts of benzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes and stirred at room temperature for 2 hours. After cooling the obtained reaction mixture in an ice bath, 45.7 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and stirred at room temperature for 30 minutes. After cooling the obtained reaction mixture in an ice bath, 34.2 parts of a 30% sodium hydroxide aqueous solution was added dropwise, and further stirred at room temperature for 30 minutes. To the obtained reaction mixture, 35.3 parts of chloroacetic acid was added dropwise at room temperature, and stirred under heating and reflux for 7 hours, and then left to cool to room temperature. The obtained reaction solution was added to 120 parts of water, and then a 200 parts of benzene and stir for 30 minutes. The obtained solution was separated into an organic layer and an aqueous layer by a liquid separation operation, and the obtained organic layer was washed with 200 parts of hydrochloric acid of an equivalent concentration, followed by washing with water, and finally with saturated saline. An appropriate amount of thenardite was added to the organic layer and stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was subjected to solvent distillation to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified light yellow liquid was dried under reduced pressure at 60°C to obtain 52.0 parts of the compound represented by formula (B-I-1). The yield is 50%

The following reaction is carried out under a nitrogen atmosphere. In a flask equipped with a condenser and a stirring device, put 9.3 parts of the compound represented by formula (BI-1), 4,4'-bis(diethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) After 10 parts and 20 parts of toluene, 14.8 parts of phosphorus oxychloride was added and stirred at 95 to 100°C for 3 hours. After cooling the obtained reaction mixture to room temperature, it was diluted with 170 parts of isopropyl alcohol. The obtained diluted reaction solution was poured into 300 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. The obtained mixture was separated into an organic layer and an aqueous layer by liquid separation operation, and the obtained organic layer was washed with saturated brine. An appropriate amount of thenardite was added to the organic layer and stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was subjected to solvent distillation to obtain a blue-purple solid. The obtained blue-violet solid was dried under reduced pressure at 60°C to obtain 19.8 parts of the compound represented by formula (A-II-1). 100% yield

Identification of the compound represented by formula (A-II-1)

(Mass analysis) ionization mode = ESI (Electronic Spray Ion, electrospray ion source) +: m/z = 601.3 [M-Cl] ⁺

Exact Mass: 636.3

The following reaction is carried out under a nitrogen atmosphere. In a flask equipped with a condenser and a stirring device, put 10 parts of the compound represented by formula (A-II-1) and 4.5 parts of lithium bis(trifluoromethanesulfonyl)imide (manufactured by Tokyo Chemical Industry Co., Ltd.) And 100 parts of N,N-dimethylformamide, stirred at 50~60℃ for 3 hours. After cooling the obtained reaction mixture to room temperature, it was added dropwise to 2000 parts of water while stirring for 1 hour, thereby obtaining a dark blue suspension. The obtained suspension was filtered to obtain a blue-green solid. The obtained blue-green solid was dried under reduced pressure at 60° C. to obtain 11.3 parts of the compound represented by formula (A-I-1). The yield is 82%

[化33]

Formula (AI-1) a compound represented by the 0.35g was dissolved in chloroform and set to the volume of 250cm ^3, wherein 2cm ³ with chloroform and the diluted volume to 100cm ³ (concentration: 0.028g / L), And the absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.9 (arbitrary unit) at λmax=628 nm.

[Synthesis Example 2]

The following reaction is carried out under a nitrogen atmosphere. Into a flask equipped with a condenser and a stirring device, 32.2 parts of potassium thiocyanate and 160 parts of acetone were added, followed by stirring at room temperature for 30 minutes. To the obtained mixture, 50 parts of 2-fluorobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes, and stirred at room temperature for 2 hours. The obtained reaction mixture was cooled in an ice bath. 40.5 parts of N-ethyl-o-toluidine (made by Tokyo Chemical Industry Co., Ltd.) was dripped at the obtained reaction mixture, and it stirred at room temperature for 30 minutes. The obtained reaction mixture was cooled in an ice bath, and 34.2 parts of a 30% sodium hydroxide aqueous solution was added dropwise, followed by stirring at room temperature for 30 minutes. To the obtained mixture, 31.3 parts of chloroacetic acid was added dropwise at room temperature, and the mixture was heated under reflux and stirred for 7 hours. Then, after the reaction mixture was left to cool to room temperature, the reaction solution was poured into 120 parts of water, and then 200 parts of toluene was added and stirred for 30 minutes. The obtained mixture was separated into an organic layer and an aqueous layer by liquid separation operation, and the obtained organic layer was washed with an equivalent concentration of hydrochloric acid, followed by washing with water, and finally with saturated brine. An appropriate amount of thenardite was added to the organic layer and stirred for 30 minutes, and then filtered to obtain a dried organic layer. Solvent distillation of the obtained organic layer, A light yellow liquid is obtained. The obtained pale yellow liquid was purified by column chromatography. The purified light yellow liquid was dried under reduced pressure at 60°C to obtain 49.9 parts of the compound represented by formula (B-I-2). Yield is 51%

The following reaction is carried out under a nitrogen atmosphere. In a flask equipped with a condenser and a stirring device, put 9.9 parts of the compound represented by formula (BI-2), 4,4'-bis(diethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) After 10 parts and 20 parts of toluene, 14.8 parts of phosphorus oxychloride was added and stirred at 95 to 100°C for 3 hours. After cooling the obtained reaction mixture to room temperature, it was diluted with 170 parts of isopropyl alcohol. The obtained diluted reaction solution was poured into 300 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. The obtained mixture was separated into an organic layer and an aqueous layer by liquid separation operation, and the obtained organic layer was washed with saturated brine. An appropriate amount of thenardite was added to the organic layer and stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer solvent was distilled off using an evaporator to obtain a blue-purple solid. The obtained blue-purple solid was purified by column chromatography. The purified blue-purple solid was dried under reduced pressure at 60°C to obtain 17.2 parts of the compound represented by formula (A-II-2). The yield is 85% [Chem 35]

Identification of the compound represented by formula (A-II-2)

(Mass analysis) ionization mode=ESI+: m/z=619.3[M-Cl] ⁺

Actual quality: 654.3

The following reaction is carried out under a nitrogen atmosphere. In a flask equipped with a condenser and a stirring device, put 10 parts of the compound represented by formula (A-II-2) and 5.7 parts of lithium bis(trifluoromethanesulfonyl)imide (manufactured by Tokyo Chemical Industry Co., Ltd.) And 30 parts of N,N-dimethylformamide, and stirred at 40°C for 3 hours. After cooling the obtained reaction mixture to room temperature, it was added dropwise to 500 parts of water while stirring for 1 hour, thereby obtaining a dark blue suspension. The obtained suspension was filtered to obtain a blue-green solid. The obtained blue-green solid was dried under reduced pressure at 60°C to obtain 11.9 parts of the compound represented by formula (A-I-2). 86% yield

Formula (AI-2) a compound represented by the 0.35g was dissolved in chloroform and set to the volume of 250cm ^3, wherein 2cm ³ with chloroform and the diluted volume to 100cm ³ (concentration: 0.028g / L), And the absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 3.1 (arbitrary unit) at λmax=630 nm.

[Synthesis Example 3]

The following reaction is carried out under a nitrogen atmosphere. After adding 23.3 parts of potassium thiocyanate and 160 parts of acetone to a flask equipped with a condenser and a stirring device, it was stirred at room temperature for 30 minutes. To the obtained mixture, 50 parts of 2-bromobenzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes, and further stirred at room temperature for 2 hours. After cooling the obtained reaction mixture in an ice bath, 29.3 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the obtained mixture, and stirred at room temperature for 30 minutes. After cooling the obtained reaction mixture in an ice bath, 34.2 parts of a 30% sodium hydroxide aqueous solution was added dropwise, and stirred at room temperature for 30 minutes. To the obtained mixture, 22.6 parts of chloroacetic acid was added dropwise at room temperature, and the mixture was heated under reflux and stirred for 7 hours. After the obtained reaction mixture was left to cool to room temperature, the reaction solution was poured into 120 parts of water, then 200 parts of toluene was added and stirred for 30 minutes. The liquid mixture is separated into an organic layer and an aqueous layer by a liquid separation operation, and the obtained organic layer is washed with an equivalent concentration of hydrochloric acid, then washed with water, and finally washed with saturated saline. An appropriate amount of thenardite was added to the obtained organic layer and stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was subjected to solvent distillation to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified light yellow liquid was dried under reduced pressure at 60°C to obtain 41.6 parts of the compound represented by formula (B-I-3). 45% yield

[化37]

The following reaction is carried out under a nitrogen atmosphere. In a flask equipped with a condenser and a stirring device, put 12.9 parts of the compound represented by formula (BI-3), 4,4'-bis(diethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) After 10 parts and 20 parts of toluene, 14.8 parts of phosphorus oxychloride was added and stirred at 95 to 100°C for 3 hours. After cooling the obtained reaction mixture to room temperature, it was diluted with 170 parts of isopropyl alcohol. The obtained diluted reaction solution was poured into 300 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. The obtained mixture was separated into an organic layer and an aqueous layer by liquid separation operation, and the obtained organic layer was washed with saturated brine. An appropriate amount of thenardite was added to the obtained organic layer and stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was subjected to solvent distillation to obtain a blue-purple solid. The obtained blue-purple solid was purified by column chromatography. The purified blue-purple solid was dried under reduced pressure at 60°C to obtain 17.6 parts of the compound represented by formula (A-II-3). 80% yield

Identification of the compound represented by formula (A-II-3)

(Mass analysis) ionization mode=ESI+: m/z=679.3[M-Cl] ⁺

Actual quality: 714.2

The following reaction is carried out under a nitrogen atmosphere. In a flask equipped with a condenser and a stirring device, put 10 parts of the compound represented by formula (A-II-3) and 5.2 parts of lithium bis(trifluoromethanesulfonyl)imide (manufactured by Tokyo Chemical Industry Co., Ltd.) And 30 parts of N,N-dimethylformamide, and stirred at 40°C for 3 hours. After cooling the obtained reaction mixture to room temperature, it was added dropwise to 500 parts of water while stirring for 1 hour, thereby obtaining a dark blue suspension. By filtering the obtained suspension, a blue-green solid was obtained. The obtained blue-green solid was dried under reduced pressure at 60°C to obtain 12.9 parts of the compound represented by formula (A-I-3). 96% yield

Reacting a compound of formula (AI-3) represented by the 0.35g was dissolved in chloroform and set to the volume of 250cm ^3, wherein 2cm ³ with chloroform and the diluted volume to 100cm ³ (concentration: 0.028g / L), And the absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.6 (arbitrary units) at λmax=632 nm.

[Synthesis Example 4]

The following reaction is carried out under a nitrogen atmosphere. In a flask equipped with a condenser and a stirring device, after adding 33 parts of potassium thiocyanate and 160 parts of acetone, the mixture was stirred at room temperature for 30 minutes. To the obtained mixture, 50.0 parts of 2-methylbenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes, and stirred at room temperature for 2 hours. After cooling the obtained reaction mixture in an ice bath, 41.6 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the obtained mixture, and stirred at room temperature for 30 minutes. After cooling the obtained reaction mixture in an ice bath, 34.2 parts of a 30% sodium hydroxide aqueous solution was added dropwise, and stirred at room temperature for 30 minutes. To the obtained mixture, 32.1 parts of chloroacetic acid was added dropwise at room temperature, followed by heating and refluxing stirring for 7 hours. The obtained reaction mixture was left to cool to room temperature, the obtained solution was poured into 120 parts of water, then 200 parts of toluene was added and stirred for 30 minutes. The liquid mixture is separated into an organic layer and an aqueous layer by a liquid separation operation, and the obtained organic layer is washed with an equivalent concentration of hydrochloric acid, then washed with water, and finally washed with saturated saline. An appropriate amount of thenardite was added to the organic layer and stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was subjected to solvent distillation to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified light yellow liquid was dried under reduced pressure at 60°C to obtain 40.5 parts of the compound represented by formula (B-I-4). 41% yield

The following reaction is carried out under a nitrogen atmosphere. In a flask equipped with a condenser and a stirring device, put 9.7 parts of the compound represented by formula (BI-4), 4,4'-bis(diethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) After 10 parts and 20 parts of toluene, 14.8 parts of phosphorus oxychloride was added and stirred at 95 to 100°C for 3 hours. The obtained reaction mixture After cooling to room temperature, it was diluted with 170 parts of isopropyl alcohol. The obtained diluted reaction solution was poured into 300 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. The obtained mixture was separated into an organic layer and an aqueous layer by liquid separation operation, and the obtained organic layer was washed with saturated brine. An appropriate amount of thenardite was added to the organic layer and stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was subjected to solvent distillation to obtain a blue-purple solid. The obtained blue-purple solid was purified by column chromatography. The purified blue-purple solid was dried under reduced pressure at 60°C to obtain 15.1 parts of the compound represented by formula (A-II-4). 75% yield

Identification of the compound represented by formula (A-II-4)

(Mass analysis) ionization mode=ESI+: m/z=615.4[M-Cl] ⁺

Actual quality: 650.3

The following reaction is carried out under a nitrogen atmosphere. In a flask equipped with a condenser and a stirring device, put 10 parts of the compound represented by formula (A-II-4) and 5.7 parts of lithium bis(trifluoromethanesulfonyl)imide (manufactured by Tokyo Chemical Industry Co., Ltd.) And 30 parts of N,N-dimethylformamide, and stirred at 40°C for 3 hours. After cooling the obtained reaction mixture to room temperature, it was added dropwise to 500 parts of water while stirring for 1 hour, thereby obtaining a dark blue suspension. The obtained suspension was filtered to obtain a blue-green solid. The obtained blue-green solid was dried under reduced pressure at 60° C. to obtain 13.2 parts of the compound represented by formula (A-I-4). 96% yield

Formula (AI-4) 0.35g of the compound represented by dissolving in chloroform and set to the volume of 250cm ^3, wherein 2cm ³ with chloroform and the diluted volume to 100cm ³ (concentration: 0.028g / L), And the absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). The compound showed an absorbance of 2.7 (arbitrary unit) at λmax=627 nm.

[Synthesis Example 5]

The following reaction is carried out under a nitrogen atmosphere. After adding 24.5 parts of potassium thiocyanate and 160 parts of acetone to a flask equipped with a condenser and a stirring device, the mixture was stirred at room temperature for 30 minutes. To the obtained mixture, 50 parts of 2-trifluoromethylbenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes, and stirred at room temperature for 2 hours. After cooling the obtained reaction mixture in an ice bath, 30.8 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the obtained mixture, and stirred at room temperature for 30 minutes. The obtained reaction mixture was cooled in an ice bath. 34.2 parts of 30% sodium hydroxide aqueous solution was added dropwise to the obtained mixture, and stirred at room temperature for 30 minutes. To the obtained mixture, 23.8 parts of chloroacetic acid was added dropwise at room temperature, and the mixture was heated under reflux and stirred for 7 hours. The obtained reaction mixture was left to cool to room temperature and poured into 120 parts of water, then 200 parts of toluene was added and stirred for 30 minutes. Separate the obtained mixture into organic layer by liquid separation operation With the water layer, the obtained organic layer is washed with an equivalent concentration of hydrochloric acid, then with water, and finally with saturated saline. An appropriate amount of thenardite was added to the obtained organic layer and stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was subjected to solvent distillation to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified light yellow liquid was dried under reduced pressure at 60°C to obtain 31.1 parts of the compound represented by formula (B-I-5). 36% yield

The following reaction is carried out under a nitrogen atmosphere. In a flask equipped with a condenser and a stirring device, 11.4 parts of the compound represented by the formula (BI-5), 4,4'-bis(diethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was put After 10 parts and 20.0 parts of toluene, 14.8 parts of phosphorus oxychloride was added and stirred at 95 to 100°C for 3 hours. After cooling the obtained reaction mixture to room temperature, it was diluted with 170 parts of isopropyl alcohol. The obtained diluted reaction solution was poured into 300 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. The obtained mixture was separated into an organic layer and an aqueous layer by liquid separation operation, and the obtained organic layer was washed with saturated brine. An appropriate amount of thenardite was added to the organic layer and stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was subjected to solvent distillation to obtain a blue-purple solid. The obtained blue-purple solid was purified by column chromatography. The purified blue-purple solid was dried under reduced pressure at 60°C to obtain 15.2 parts of the compound represented by formula (A-II-5). 70% yield

[化44]

Identification of the compound represented by formula (A-II-5)

(Mass analysis) ionization mode=ESI+: m/z=669.3[M-Cl] ⁺

Actual quality: 704.3

The following reaction is carried out under a nitrogen atmosphere. In a flask equipped with a condenser and a stirring device, put 10 parts of the compound represented by formula (A-II-5) and 4.1 parts of lithium bis(trifluoromethanesulfonyl)imide (manufactured by Tokyo Chemical Industry Co., Ltd.) And 30.0 parts of N,N-dimethylformamide, followed by stirring at 40°C for 3 hours. After cooling the obtained reaction mixture to room temperature, it was added dropwise to 500 parts of water while stirring for 1 hour, thereby obtaining a dark blue suspension. By filtering the obtained suspension, a blue-green solid was obtained. The obtained blue-green solid was dried under reduced pressure at 60° C. to obtain 11.4 parts of the compound represented by formula (A-I-5). 85% yield

[化45]

Reacting a compound of formula (AI-5) represented by the 0.35g was dissolved in chloroform and set to the volume of 250cm ^3, wherein 2cm ³ with chloroform and the diluted volume to 100cm ³ (concentration: 0.028g / L), And the absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 1.9 (arbitrary unit) at λmax=631 nm.

[Synthesis Example 6]

The following reaction is carried out under a nitrogen atmosphere. In a flask equipped with a condenser and a stirring device, 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N,N-dimethylformamide were added, and the mixed solution was cooled in an ice bath. Under ice-cooling, 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was gradually added in small amounts over 30 minutes, and the mixture was stirred for 1 hour while warming to room temperature. 10.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was gradually added to the reaction liquid in small amounts, and stirred at room temperature for 24 hours. After gradually adding a small amount of the reaction solution to 200 parts of ice water, it was allowed to stand at room temperature for 15 hours. If the water was removed by decantation, a viscous solid could be obtained 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 out the precipitated solid, it was purified by column chromatography. The purified light yellow solid was dried under reduced pressure at 60°C to obtain 9.8 parts of the compound represented by formula (C-I-18).

[化46]

The following reaction is carried out under a nitrogen atmosphere. In a flask equipped with a condenser and a stirring device, put 8.2 parts of the compound represented by formula (BI-2), 10 parts of the compound represented by formula (CI-18) and 20 parts of toluene, and then add phosphorus oxychloride 12.2 parts and stir at 95~100℃ for 3 hours. Then, after cooling the reaction mixture to room temperature, it was diluted with 170 parts of isopropyl alcohol. Then, the diluted reaction solution was poured into 300 parts of saturated brine, then 100 parts of toluene was added and stirred for 30 minutes. Then, the stirring was stopped, and it was allowed to stand for 30 minutes. As a result, it was separated into an organic layer and an aqueous layer. After discarding the water layer by liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of thenardite was added to the organic layer and stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer solvent was distilled off using an evaporator to obtain a blue-purple solid. Furthermore, the blue-purple solid was dried under reduced pressure at 60° C. to obtain 18.4 parts of the compound represented by formula (A-II-18).

The following reaction is carried out under a nitrogen atmosphere. In a flask equipped with a condenser and a stirring device, 8 parts of the compound represented by the formula (A-II-18) and 396 parts of methanol were put, and stirred at room temperature for 30 minutes to prepare a blue solution. Then, after adding 396 parts of water to the blue solution, it was further stirred at room temperature for 30 minutes to obtain a reaction solution.

In a beaker, 53 parts of water was put, and further, 11.8 parts of Kejin-type phosphotungstic acid (manufactured by Aldrich) and 53 parts of methanol were put into the water, and mixed in an air environment at room temperature to prepare phosphotungstic acid Solution.

The obtained phosphotungstic acid solution was added dropwise to the first prepared reaction solution over 1 hour. It was further stirred at room temperature for 30 minutes, and then filtered to obtain a blue solid. The obtained blue solid was put into 200 parts of methanol and dispersed for 1 hour, and then the operation of filtering was repeated twice. The blue solid obtained by this operation was poured into 200 parts of water and dispersed for 1 hour, and then the operation of filtering was repeated twice. The blue solid obtained by this operation was dried under reduced pressure at 60° C. to obtain 17.1 parts of the compound represented by formula (A-I-18).

Formula (AI-18) The compound represented 0.35g was dissolved in chloroform and set to the volume of 250cm ^3, wherein the use of chloroform and 2cm ³ was diluted to a volume of 100cm ³ (concentration: 0.028g / L), And the absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 1.1 (arbitrary unit) at λmax=626 nm.

[Synthesis Example 7]

Nitrogen was circulated at 0.02 L/min in a flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel to create a nitrogen atmosphere. 305 parts of propylene glycol monomethyl ether acetate were added, and the mixture was heated to 70°C with stirring. Then, 60 parts of acrylic acid and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate (50:50 in molar ratio) were used to represent the compound represented by formula (I-1) and formula (II- 1) The compound represented was mixed) 440 parts were dissolved in 140 parts of propylene glycol monomethyl ether acetate to prepare a solution, and the dissolved drops were added to a flask kept at 70°C for 4 hours using a dropping funnel.

On the other hand, using another dropping funnel for 4 hours, 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts of propylene glycol monomethyl ether acetate The resulting solution was added dropwise to the flask. After the dropping of the solution of the polymerization initiator was completed, the temperature 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 molecular weight distribution of 2.16, and a solid content of 34.8 %, a resin B1 solution with an acid value of 81 mg-KOH/g in terms of solid content conversion. Resin B1 has the structural units shown below.

[化50]

[Synthesis Example 8]

An appropriate amount of nitrogen was circulated in a flask equipped with a reflux condenser, a dropping funnel, and a stirrer and replaced with a nitrogen atmosphere. 371 parts by weight of propylene glycol monomethyl ether acetate was added, and heated to 85°C while stirring. Then, over a period of 4 hours, 54 parts by weight of acrylic acid, 225 parts by weight of a mixture of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]-8 or/and 9-decyl acrylate, vinyl toluene ( Isomer mixture) A mixed solution of 81 parts by weight and 80 parts by weight of propylene glycol monomethyl ether acetate.

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

The weight average molecular weight (Mw) and number average score of the resins obtained in Synthesis Examples 7 and 8 The measurement of the molecular weight (Mn) was carried out using GPC (Gel Permeation Chromatography) method under the following conditions.

Device: K2479 (made by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40℃

Solvent: THF (Tetrahydrofuran, Tetrahydrofuran)

Flow rate: 1.0mL/min

Detector: RI (Refractive Index, refractive index) calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio (Mw/Mn) of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained in the above is defined as the molecular weight distribution.

Preparation Example 1 <Preparation of Dispersion Liquid (1)>

By mixing 10 parts of the compound represented by formula (AI-18), 2 parts of dispersant (BYK (registered trademark)-LPN6919 (manufactured by BYK-Chemie Japan)), 4 parts of resin B2 (conversion of solid content) and propylene glycol 84 parts of monomethyl ether acetate were mixed, and the compound represented by the formula (AI-18) was sufficiently dispersed using a bead mill to obtain a dispersion liquid (1).

Examples 1 to 12 and Comparative Example 1 <Preparation of colored curable resin composition>

The components of Table 3 and Table 4 were mixed to obtain a colored curable resin composition. In Tables 3 and 4, the resin fraction indicates the value converted from the solid content.

In addition, in Table 3 and Table 4, each component shows the following.

Blue dye (A):

A1: Compound represented by formula (A-I-1)

A2: Compound represented by formula (A-I-2)

A3: Compound represented by formula (A-I-3)

A4: Compound represented by formula (A-I-4)

A5: Compound represented by formula (A-I-5)

Resin (B): Resin B1

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (D): N-benzyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF company Manufacturing; O-acyl oxime compounds)

Thiol compound (T): pentaerythritol tetrathiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)

磷環庚烷(Sumilizer(註冊商標)GP；住友化學股份有限公司製造) Antioxidant (G): 6-[3-(3-tertiarybutyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tertiarybutyldi Benzo[d,f][1,3,2]di

Phosphocycloheptane (Sumilizer (registered trademark) GP; manufactured by Sumitomo Chemical Co., Ltd.)

Silsesquioxane compound (H): H1; Compoceran (registered trademark) SQ109; manufactured by Arakawa Chemical Industry Co., Ltd.

Silsesquioxane compound (H): H2; AC-SQ TA-100; manufactured by East Asia Synthetic Co., Ltd.

Solvent (E): E1: propylene glycol monomethyl ether acetate

Solvent (E): E2: 4-hydroxy-4-methyl-2-pentanone

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

<production of coloring pattern>

On a 5 cm square glass substrate (Eagle XG; manufactured by Corning), a colored curable resin composition was applied by spin coating, and then prebaked at 100°C for 3 minutes to form a coloring composition layer. After leaving to cool, the distance between the substrate on which the coloring composition layer is formed and the reticle made of quartz glass is set to 100 μm, using an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) in an atmospheric environment at 150 mJ/cm ² The amount of exposure (365 nm reference) was irradiated with light. A mask formed with a 100 μm line and gap pattern was used. The coloring composition layer after light irradiation is immersed and developed in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 25°C for 80 seconds, after washing with water, in an oven at 230°C After 20 minutes of post-baking, a colored pattern was obtained.

<Measurement of film thickness>

For the obtained coloring pattern, the film thickness was measured using a film thickness measuring device (DEKTAK3; manufactured by Japan Vacuum Technology Co., Ltd.). The results are shown in Table 5.

<Chemical resistance evaluation>

The obtained coloring pattern was measured using a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the characteristic function of the C light source was used in the XYZ color system of CIE (Commission International Eclairage). The xy chromaticity coordinates (x, y) and tristimulus value Y were measured.

The obtained coloring pattern was immersed in N-methylpyrrolidone at 23°C for 40 minutes. After dipping, the xy chromaticity coordinates (x, y) and Y are measured in the same manner as before dipping, and the color difference is calculated by the method described in JIS Z 8730:2009 (7. Color difference calculation method) based on the measured value Eab*. Using the ΔEab* of the color-curing composition obtained in Comparative Example 1 as a reference, the chemical resistance improvement rate was calculated according to the following formula. The results are shown in Table 5.

Improvement rate (%)={(△Eab* of Comparative Example 1-△Eab* of Example)/△Eab* of Comparative Example 1}×100

Example 13 to Example 16 and Comparative Example 2 <Preparation of colored curable resin composition>

The components of Table 6 were mixed to obtain a colored curable resin composition. In Table 6, the fraction of resin represents the value converted from the solid content.

In addition, in Table 6, each component shows the following.

Blue dye (A); A6: C.I. Basic Blue 7 (Tokyo Chemical Co., Ltd., maximum absorption wavelength in chloroform solution; 631nm)

Resin (B): Resin B1

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (D): N-benzyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF company Manufacturing; O-acyl oxime compounds)

Thiol compound (T): pentaerythritol tetrathiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)

磷環庚烷(Sumilizer(註冊商標)GP；住友化學股份有限公司製造) Antioxidant (G): 6-[3-(3-tertiarybutyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tertiarybutyldi Benzo[d,f][1,3,2]di

Phosphocycloheptane (Sumilizer (registered trademark) GP; manufactured by Sumitomo Chemical Co., Ltd.)

Silsesquioxane compound (H): H1; Compoceran (registered trademark) SQ109; manufactured by Arakawa Chemical Industry Co., Ltd.

Solvent (E): E1: propylene glycol monomethyl ether acetate

Solvent (E): E2: 4-hydroxy-4-methyl-2-pentanone

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

A colored pattern was produced in the same manner as in Example 1, and chemical resistance evaluation was performed. Will compare The △Eab* of the color-curing composition obtained in Comparative Example 2 was used as a reference, and the improvement rate of chemical resistance was calculated according to the following formula. The results are shown in Table 7.

Improvement rate (%)={(△Eab* of Comparative Example 2-△Eab* of Example)/△Eab* of Comparative Example 2}×100

Examples 17 to 20 and Comparative Example 3 <Preparation of colored curable resin composition>

The components of Table 8 were mixed to obtain a colored curable resin composition. In Table 8, the fraction of resin represents the value converted from the solid content.

In addition, in Table 8, each component shows the following.

Blue dye (A);

A7: Mixture of compounds represented by formula (3-1), formula (3-2), formula (3-3) and formula (3-4) Substance (prepared by the method according to the synthesis example of Japanese Patent No. 3961078. Maximum absorption wavelength in chloroform solution; 594nm)

Resin (B): Resin B1

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (D): N-benzyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF company Manufacturing; O-acyl oxime compounds)

Thiol compound (T): pentaerythritol tetrathiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)

磷環庚烷(Sumilizer(註冊商標)GP；住友化學股份有限公司製造) Antioxidant (G): 6-[3-(3-tertiarybutyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tertiarybutyldi Benzo[d,f][1,3,2]di

Phosphocycloheptane (Sumilizer (registered trademark) GP; manufactured by Sumitomo Chemical Co., Ltd.)

Silsesquioxane compound (H): H1; Compoceran (registered trademark) SQ109; manufactured by Arakawa Chemical Industry Co., Ltd.

Solvent (E): E1: propylene glycol monomethyl ether acetate

Solvent (E): E2: 4-hydroxy-4-methyl-2-pentanone

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

A colored pattern was produced in the same manner as in Example 1, and chemical resistance evaluation was performed. Using the △Eab* of the color-curing composition obtained in Comparative Example 3 as a reference, the chemical resistance improvement rate was calculated according to the following formula. The results are shown in Table 9.

Improvement rate (%) = {(△Eab* of Comparative Example 3-△Eab* of Example)/△Eab* of Comparative Example 3}×100

Examples 21 to 24 and Comparative Example 4 <Preparation of colored curable resin composition>

The components of Table 10 were mixed to obtain a colored curable resin composition. In Table 10, The resin fraction represents the value converted from the solid content.

In addition, in Table 10, each component shows the following.

Blue dye (A): A8; CERAFIS BLUE 603 (manufactured by Orient Chemical Industry Co., Ltd., maximum absorption wavelength in chloroform solution; 611nm)

Resin (B): Resin B1

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (D): N-benzyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF company Manufacturing; O-acyl oxime compounds)

Thiol compound (T): pentaerythritol tetrathiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)

磷環庚烷(Sumilizer(註冊商標)GP；住友化學股份有限公司製造) Antioxidant (G): 6-[3-(3-tertiarybutyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tertiarybutyldi Benzo[d,f][1,3,2]di

Phosphocycloheptane (Sumilizer (registered trademark) GP; manufactured by Sumitomo Chemical Co., Ltd.)

Silsesquioxane compound (H): H2; AC-SQTA-100; manufactured by East Asia Synthetic Co., Ltd.)

Solvent (E): E1: propylene glycol monomethyl ether acetate

Solvent (E): E2: 4-hydroxy-4-methyl-2-pentanone

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

A colored pattern was produced in the same manner as in Example 1, and chemical resistance evaluation was performed. Using the ΔEab* of the color-curing composition obtained in Comparative Example 4 as a reference, the chemical resistance improvement rate was calculated according to the following formula. The results are shown in Table 11.

Improvement rate (%)={(△Eab* of Comparative Example 4-△Eab* of Example)/△Eab* of Comparative Example 4}×100

Examples 25 to 28 and Comparative Example 5 <Preparation of colored curable resin composition>

The components of Table 12 were mixed to obtain a colored curable resin composition. In Table 12, the fraction of resin represents the value converted from the solid content.

In addition, in Table 12, each component shows the following.

Blue dye (A): A9; C.I. Solvent Blue 45 (Savinyl Blue RS; manufactured by Clariant, maximum absorption wavelength in chloroform solution; 625 nm)

Resin (B): Resin B1

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (D): N-benzyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF company Manufacturing; O-acyl oxime compounds)

Thiol compound (T): pentaerythritol tetrathiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)

磷環庚烷(Sumilizer(註冊商標)GP；住友化學股份有限公司製造) Antioxidant (G): 6-[3-(3-tertiarybutyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tertiarybutyldi Benzo[d,f][1,3,2]di

Phosphocycloheptane (Sumilizer (registered trademark) GP; manufactured by Sumitomo Chemical Co., Ltd.)

Silsesquioxane compound (H): H1; Compoceran (registered trademark) SQ109; manufactured by Arakawa Chemical Industry Co., Ltd.

Solvent (E): E1: propylene glycol monomethyl ether acetate

Solvent (E): E2: 4-hydroxy-4-methyl-2-pentanone

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

A colored pattern was produced in the same manner as in Example 1, and the obtained colored pattern was immersed in N-methylpyrrolidone at 40°C for 30 minutes to perform chemical resistance evaluation. Using the △Eab* of the color-curing composition obtained in Comparative Example 5 as a reference, the chemical resistance improvement rate was calculated according to the following formula. The results are shown in Table 13.

Improvement rate (%)={(△Eab* of Comparative Example 5-△Eab* of Example)/△Eab* of Comparative Example 5}×100

Examples 29 to 32 and Comparative Example 6 <Preparation of colored curable resin composition>

The components of Table 14 were mixed to obtain a colored curable resin composition. In the table, the fraction of resin represents the value converted from the solid content.

In addition, in Table 14, each component shows the following.

Dispersion (1): The dispersion (1) prepared in Preparation Example 1

Resin (B): Resin B2

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (D): N-benzyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF company Manufacturing; O-acyl oxime compounds)

Thiol compound (T): pentaerythritol tetrathiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)

Silsesquioxane compound (H): H1; Compoceran (registered trademark) SQ109; manufactured by Arakawa Chemical Industry Co., Ltd.

Solvent (E): E1: propylene glycol monomethyl ether acetate

Solvent (E): E3: Propylene glycol monomethyl ether

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

<Chemical resistance evaluation>

Use the color measuring machine (OSP-SP-200; Olympus shares) for the obtained coloring pattern Co., Ltd.) Measure the spectrometry and use the characteristic function of the C light source to measure the xy chromaticity coordinates (x, y) and tristimulus value Y in the XYZ color system of CIE.

The obtained coloring pattern was immersed in N-methylpyrrolidone at 23°C for 30 minutes. After dipping, the xy chromaticity coordinates (x, y) and Y are measured in the same manner as before dipping, and the color difference is calculated by the method described in JIS Z 8730:2009 (7. Color difference calculation method) based on the measured value Eab*. Using the ΔEab* of the color-curing composition obtained in Comparative Example 6 as a reference, the chemical resistance improvement rate was calculated according to the following formula. The results are shown in Table 15.

Improvement rate (%) = {(△Eab* of Comparative Example 6-△Eab* of Example)/△Eab* of Comparative Example 6}×100

Examples 33 to 36 and Comparative Example 7 <Preparation of colored curable resin composition>

The components of Table 16 were mixed to obtain a colored curable resin composition. In the table, the fraction of resin represents the value converted from the solid content.

In addition, in Table 16, each component shows the following.

Dispersion (1): The dispersion (1) prepared in Preparation Example 1

Blue dye (A); A7: mixture of compounds represented by formula (3-1), formula (3-2), formula (3-3) and formula (3-4)

Resin (B): Resin B2

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (D): N-benzyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF company Manufacturing; O-acyl oxime compounds)

Thiol compound (T): pentaerythritol tetrathiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)

Silsesquioxane compound (H): H2; AC-SQ TA-100; manufactured by East Asia Synthetic Co., Ltd.

Solvent (E): E1: propylene glycol monomethyl ether acetate

Solvent (E): E3: Propylene glycol monomethyl ether

Leveling agent (F): polyether modified polysiloxane oil (Toray Silicone SH8400; Dow (Made by Corning Toray Co., Ltd.)

<Chemical resistance evaluation>

For the obtained coloring pattern, use a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.) to measure the spectrophotometry, and use the characteristic function of the C light source to the xy chromaticity coordinates (x, y) in the XYZ color system of CIE ) Measured with tristimulus value Y

The obtained coloring pattern was immersed in N-methylpyrrolidone at 40°C for 30 minutes. After dipping, the xy chromaticity coordinates (x, y) and Y are measured in the same manner as before dipping, and the color difference is calculated by the method described in JIS Z 8730:2009 (7. Color difference calculation method) based on the measured value Eab*. Using the ΔEab* of the color-curing composition obtained in Comparative Example 7 as a reference, the chemical resistance improvement rate was calculated according to the following formula. The results are shown in Table 17.

Improvement rate (%)={(△Eab* of Comparative Example 7-△Eab* of Example)/△Eab* of Comparative Example 7}×100

Examples 37-40 and Comparative Example 8 <Preparation of colored curable resin composition>

The components of Table 18 were mixed to obtain a colored curable resin composition. In the table, the fraction of resin represents the value converted from the solid content.

In addition, in Table 18, each component shows the following.

Blue dye (A); A2: compound represented by formula (A-I-2)

染料(X)；X1：式(X-1)所表示之化合物(藉由依據日本專利特開2013-253168之實施例之方法進行合成)

Dye (X); X1: compound represented by formula (X-1) (synthesized by the method according to the example of Japanese Patent Laid-Open No. 2013-253168)

Resin (B): Resin B1

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (D): N-benzyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF company Manufacturing; O-acyl oxime compounds)

Thiol compound (T): pentaerythritol tetrathiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)

磷環庚烷(Sumilizer(註冊商標)GP；住友化學股份有限公司製造) Antioxidant (G): 6-[3-(3-tertiarybutyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tertiarybutyldi Benzo[d,f][1,3,2]di

Phosphocycloheptane (Sumilizer (registered trademark) GP; manufactured by Sumitomo Chemical Co., Ltd.)

Silsesquioxane compound (H): H2; AC-SQ TA-100; manufactured by East Asia Synthetic Co., Ltd.

Solvent (E): E1: propylene glycol monomethyl ether acetate

Solvent (E): E2: 4-hydroxy-4-methyl-2-pentanone

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

<Chemical resistance evaluation>

For the obtained coloring pattern, use a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.) to measure the spectrophotometry, and use the characteristic function of the C light source to the xy chromaticity coordinates (x, y) in the XYZ color system of CIE ) Measured with the tristimulus value Y.

The obtained coloring pattern was immersed in N-methylpyrrolidone at 40°C for 30 minutes. After dipping, the xy chromaticity coordinates (x, y) and Y are measured in the same manner as before dipping, and the color difference is calculated by the method described in JIS Z 8730:2009 (7. Color difference calculation method) based on the measured value Eab*. Using the ΔEab* of the color-curing composition obtained in Comparative Example 8 as a reference, the chemical resistance improvement rate was calculated according to the following formula. The results are shown in Table 19.

Improvement rate (%) = {(△Eab* of Comparative Example 8-△Eab* of Example)/△Eab* of Comparative Example 8}×100

[Industry availability]

The invention provides a color-curable resin composition capable of forming a color filter with good chemical resistance.

Claims (5)

A color-curing resin composition containing blue dye, resin, polymerizable compound, polymerization initiator and silsesquioxane compound, wherein the content of silsesquioxane compound relative to 100 parts by mass of blue dye is 25~2000 parts by mass, where the blue dye contains the compound represented by formula (A-II),

[In formula (A-II), [Y ² ] ^m- represents an arbitrary m-valent anion; R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a C 1-20 saturated hydrocarbon group which may be substituted, A group having an oxygen atom inserted between the carbon atoms of the alkyl group of 2 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 to these The bonded nitrogen atoms form a ring together, and R ⁴³ and R ⁴⁴ can be bonded to form a ring together with the bonded nitrogen atoms; R ⁴⁵ to R ⁵² independently represent a hydrogen atom, a halogen atom, a nitro group, and a hydroxyl group , A saturated hydrocarbon group having 1 to 8 carbon atoms, or a group having an oxygen atom inserted between carbon atoms constituting an alkyl group having 2 to 8 carbon atoms, or R ⁴⁶ and R ⁵⁰ may be bonded to each other to form -O-,- NH-, -S- or -SO ₂ -; R ⁵³ and R ⁵⁴ independently represent a hydrogen atom, a C 1-20 saturated hydrocarbon group which may be substituted, and a carbon atom constituting an alkyl group having 2 to 20 carbon atoms A group with an oxygen atom interposed therebetween, an aryl group which may be substituted, or an aralkyl group which may be substituted; R ⁵⁵ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aryl group which may be substituted. X represents an oxygen atom, -NR ⁵⁷ -or sulfur atom; R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; in the case where the compound represented by formula (A-II) contains a plurality of cations, the plurality of The cations may have the same structure as each other or different structures; m represents an arbitrary natural number]. The color-curable resin composition according to claim 1, wherein the blue dye further comprises at least one dye selected from the group consisting of phthalocyanine dye, anthraquinone dye, cyanine dye, porphyrin dye, and thiazole dye. The color-curable resin composition according to claim 1, wherein the blue dye is a compound having an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and an oxygen atom. A color filter formed from the color-curable resin composition according to any one of claims 1 to 3. A display device including the color filter according to claim 4.