TWI736597B - Colored curable resin composition, color filter, and display device having the same - Google Patents

Abstract

A colored curable resin composition comprises a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and an extender pigment (P), wherein the colorant (A) includes a lake pigment.

Description

Colored curable resin composition, color filter and display device containing the color filter

The present invention relates to a colored curable resin composition, a color filter, and a display device containing the color filter.

Known is a coloring and curable resin composition comprising a coloring agent containing dyes and pigments, an extender pigment and a dispersing agent dispersed in a solvent containing propylene glycol monomethyl ether acetate, a polymerizable compound, and a polymerization initiator.物 (Japanese Patent Application Publication No. 2015-98590).

The present invention provides the following colored curable resin composition, color filter, and display device.

[1] A coloring and curable resin composition containing a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and an extender pigment (P), wherein the colorant (A) contains Lake pigments.

[2] The coloring and curable resin composition according to [1], wherein the lake pigment is an anion containing a compound containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen, and a pigment Skeleton's Yang Li Compound (Aa) composed of sons.

[3] The colored curable resin composition according to [2], wherein the aforementioned compound (Aa) is a compound represented by formula (AI), [X ⁺ ] _m [Y] ^m- (AI)

[In formula (AI), X ⁺ represents the cation represented by formula (AIX);

[Y] ^m- represents an m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen; m represents any natural number; in formula (AIX), R ⁴¹ to R ^{44 are} mutually Independently represent a monovalent saturated hydrocarbon group with 1 to 20 carbons, an alkyl group with 2 to 20 carbons which may have a substituent, and a group in which an oxygen atom is inserted between the methylene groups constituting the alkyl group (but a plurality of oxygen atoms will not (Inserted in a contiguous manner), a monovalent aromatic hydrocarbon group having 6 to 14 carbons which may have a substituent, an aralkyl group having 7 to 11 carbons which may have a substituent or a hydrogen atom; R ⁴¹ and R ⁴² may be bonded , And together with these bonded nitrogen atoms to form a ring, R ⁴³ and R ⁴⁴ can be bonded, and together with these bonded nitrogen atoms to form a ring; R ⁴⁷ to R ⁵⁴ independently represent a hydrogen atom, Halogen atom, nitro group, hydroxyl group or C1-C8 alkyl group. When the carbon number is 2 or more, oxygen atoms can be inserted between the methylene groups constituting the alkyl group (but the plural oxygen atoms will not be adjacent to each other). Insert); R ⁴⁸ and R ⁵² bond to each other to form -NH-, -O-, -S- or -SO ₂ -; T ¹ represents a monovalent aromatic heterocyclic group which may have a substituent; m is 2 or more When it is a natural number, the plural X ⁺ can have the same structure or different structures].

[4] The colored curable resin composition according to any one of [1] to [3], wherein the extender pigment (P) is at least one selected from the group consisting of zinc oxide, titanium oxide, silicon oxide, and zirconium oxide 1 kind.

[5] A color filter formed of the coloring curable resin composition as described in any one of [1] to [4].

[6] A display device including the color filter as described in [5].

<Colored curable resin composition>

The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and an extender pigment (P), wherein the colorant (A) contains a color Lake pigment.

According to the colored curable resin composition of the present invention containing the colorant (A) and the extender pigment (P), the solvent resistance and heat resistance of the cured film (color filter, etc.) can be improved.

Furthermore, in this specification, the compound as each component is exemplified Unless otherwise specified, they can be used alone or in combination.

[1] Coloring agent (A) [1-1] Lake Pigment

The colorant (A) contains lake pigments.

In this specification, the so-called lake pigment refers to a pigment in which a soluble dye becomes insoluble in water or an organic solvent through a lake-forming agent. The pigment has a solubility (23°C) of, for example, propylene glycol monomethyl ether acetate or propylene glycol monomethyl ether of 1% by mass or less.

Dyes that can form lake pigments, such as acid dyes, basic dyes, direct dyes, etc., can be used in color index (published by The Society of Dyers and Colorists) other than pigments classified as having hue Compounds, known dyes described in Dyeing Notes (Sei Dye Company).

As specific examples of acid dyes, for example, CI (Color Index) Acid Red 1, 3, 4, 6, 8, 11, 12, 14, 18, 26, 27, 33, 37, 50, 51, 51:1, 52 , 53, 57, 82, 87, 88, 91, 92, 93, 94, 95, 98, 101, 103, 106, 108, 111, 114, 131, 137, 138, 151, 154, 158, 159, 173 , 184, 186, 215, 257, 266, 289, 296, 337; CI acid orange 7, 10, 11, 12, 15, 19, 20, 22, 28, 30, 52, 56, 74, 127; CI acid Violet 9, 11, 15, 16, 17, 19, 21, 23, 24, 25, 30, 38, 41, 42, 43, 49, 50, 56, 58, 72; CI Acid Yellow 1, 3, 17, 18, 23, 25, 36, 38, 42, 44, 54, 59, 72, 78, 151; CI Acid Brown 2, 4, 13, 19, 248; CI Acid Blue 1, 3, 5, 7, 9, 11, 13, 14, 15, 17, 18, 19, 20, 22, 24, 25, 34, 38, 40, 45, 48, 59, 61 , 74, 75, 78, 80, 83, 86, 88, 90, 91, 92, 93, 93: 1, 97, 98, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117 , 119, 121, 123, 126, 127: 1, 129, 142, 145, 147, 167, 213, 230, 269; CI Acid Green 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 25, 27.

As specific examples of basic dyes, for example, CI Basic Red 1, 1: 1, 2, 3, 4, 5, 6, 8, 9, 10, 11, 12, 13, 14, 15, 17, 22, 23 , 25, 27, 29, 30, 32, 34, 37, 38, 39, 46, 46: 1, 51, 52, 53, 54, 55, 62, 64, 76, 82, 90, 94, 118; CI Basic Orange 1, 2, 4, 5, 14, 15, 16, 17, 18, 21, 22, 23, 24, 25, 29, 30, 33, 54, 69; CI Basic Violet 1, 2, 3 , 4, 5, 6, 7, 8, 10, 11, 11:1, 12, 13, 14, 15, 16, 18, 20, 21, 22, 23, 28, 36, 39; CI Basic Yellow 1 , 2, 3, 5, 6, 7, 9, 11, 11:1, 13, 14, 15, 19, 20, 21, 23, 24, 25, 28, 29, 32, 36, 37, 38, 39 , 40, 41, 45, 49, 51, 52, 53, 57, 62, 73, 80, 90; CI Basic Brown 1, 16, 17, 18; CI Basic Blue 1, 2, 3, 5, 6 , 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 22, 23, 24, 25, 26, 35, 41, 44, 45, 47, 53, 54 , 55, 64, 65, 66, 67, 72, 74, 81, 99, 129; CI Basic Green 1, 4, 5.

As specific examples of direct dyes, for example, C.I. Direct Blue 41, 77, 86, 87, 106, 107, 108, 109, 189, 190, 199, 264; C.I. Direct Purple 54.

As specific examples of lake-forming agents, for example, barium chloride, calcium chloride, ammonium sulfate, aluminum chloride, aluminum acetate, lead acetate, tannic acid, Catanol, Tamol, heteropoly acid (phosphotungstic acid, phosphomolybdic acid , Phosphotungstomolybdic acid, silicotungstic acid, silicomolybdic acid, silicotungstomolybdic acid, etc.), heteropoly acid (tungstic acid, molybdic acid, etc.).

As specific lake pigments, for example, CI Pigment Blue 1, 1: 2, 2, 3, 8, 9, 10, 11, 12, 14, 17: 1, 18, 19, 24, 24: 1, 53, 56 , 61, 62, 63, 78; CI Pigment Violet 1, 2, 2: 2, 3, 3: 1, 3: 3, 3: 4, 4, 5, 5: 1, 6: 1, 7: 1, 9, 12, 20, 26, 27, 39; CI Pigment Green 1, 2, 3, 4, 8, 9, 10, 12, 45; CI Pigment Red 48: 1, 48: 2, 48: 3, 48: 4. 48: 5, 49, 49: 1, 49: 2, 49: 3, 50, 50: 1, 51, 52: 1, 52: 2, 53, 53: 1, 53: 3, 57: 1, 58, 58: 1, 58: 2, 58: 3, 58: 4, 60: 1, 63, 63: 1, 63: 2, 63: 3, 64: 1, 68, 81, 81: 1, 81: 2. 81: 3, 81: 4, 82, 83, 84, 90, 90: 1, 151, 169, 172, 173, 174, 191, 193, 200, 237, 239, 247; CI Pigment Orange 17, 18 , 19, 46; CI Pigment Yellow 18, 61, 61: 1, 62, 100, 104, 115, 133, 168, 169, 183, 191, 209, 209: 1, 212, etc.

The lake pigment of the present invention may have cations derived from the above-mentioned dyes, or may have anions derived from the above-mentioned dyes. The lake pigment preferably has cations derived from the above-mentioned dyes.

As the cation derived from the above-mentioned dye, for example, a cation derived from a triarylmethane dye, a Rhodamine dye, a xanthene dye, and the like. The cations from the above dyes are more It is desirably a triarylmethane-based dye, and more desirably a triarylmethane-based dye that may have a heterocyclic ring such as a thiazolyl group.

When the lake pigment has a cation derived from the dye, it usually has an anion such as a transition metal atom, a silicon atom, an aluminum atom, a boron atom, a sulfur atom, and a halogen atom.

As the anion of the lake pigment, in addition to heteropoly acid ion (M _m1 O _n ) ^c- , heteropoly acid ion (X ₁ M _m1 O _n ) ^c- (in each formula, M represents a polyatom, X represents a heteroatom, 1 represents the composition ratio of heteroatoms, m1 represents the composition ratio of polyatoms, and n represents the composition ratio of oxygen atoms. c represents an integer from 1 to 8), such as the following anions.

(In the formula, M represents a boron atom or an aluminum atom. R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently represent a hydroxyl group, a hydrogen atom, an alkoxy group having 1 to 4 carbons, and an alkyl group having 1 to 4 carbons. Or a reactive group. However, ^{at least one of R 61} , R ⁶² , R ⁶³ and R ⁶⁴ is a reactive group.)

[In formula (6), W ³ and W ⁴ each independently represent a fluorine atom or a fluoroalkyl group having 1 to 4 carbons, or W ³ and W ^{4 are} bonded to form a fluoroalkanediyl group having 1 to 4 carbons. ]

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

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

[In the formula (9), Y ² represents a fluoroalkanediyl group having 1 to 4 carbon atoms. ]

From the standpoint of solvent resistance and heat resistance, the lake pigment contains selected from tungsten (W), molybdenum (Mo), vanadium (V), titanium (Ti), niobium (Nb), silicon (Si), phosphorus ( P), arsenic (As), sulfur (S), iron (Fe), and cobalt (Co) are composed of anions of at least one element and oxygen compound and a compound (AA) composed of a cation with a pigment skeleton. Desirably, a compound (Aa) composed of an anion of a compound containing at least one element selected from the group consisting of W, Mo, Si, and P and oxygen and a cation having a dye skeleton is more desirable.

The lake pigments of the present invention are more preferably basic dyes (triarylmethane dyes, rose bengal dyes, etc.) and polyacid lake pigments.

The polyacid is a condensed acid of plural oxo acids, which can be a heteropoly acid ion (M _m1 O _n ) ^c- or a heteropoly acid ion (X ₁ M _m1 O _n ) ^c- . In the formula, M represents polyatoms, X represents heteroatoms, 1 represents the composition ratio of heteroatoms, m1 represents the composition ratio of polyatoms, n represents the composition ratio of oxygen atoms, and c represents an integer from 1 to 8.

As the polyatomic M, for example, W, Mo, V, Ti, Nb and the like.

As the heteroatom X, for example, Si, P, As, S, Fe, Co etc.

From the viewpoints of solvent resistance and heat resistance, specific examples of preferable polyacids include heteropolyacids such as _{tungstate ion [W 10} O ₃₂ ] ^4- and molybdate ion [Mo ₆ O ₁₉ ] ^2- ; Phosphotungstic acid ion [PW ₁₂ O ₄₀ ] ^3- , silicotungstic acid ion [SiW ₁₂ O ₄₀ ] ^4- , phosphomolybdate ion [PMo ₁₂ O ₄₀ ] ^3- , phosphotungstomolybdate ion [PW _12-x Mo _x O ₄₀ ] ^3- , H ₃ [PW _2-x Mo _x O ₇ ] ^4- and other heteropoly acids. More specifically, for example, phosphotungstomolybdate ions [PW ₁₀ Mo ₂ O ₄₀ ] ^3- , [PW ₁₁ Mo ₁ O ₄₀ ] ^3- , and phosphotungstic acid ions [PW ₁₂ O ₄₀ ] ^3- .

Among them, from the viewpoints of solvent resistance, heat resistance, etc., the compound (Aa) is preferably a compound represented by the ^{formula (AI): [X +} ] _m [Y] ^{m- (AI).}

In formula (AI), X ⁺ represents the cation represented by formula (AIX);

[Y] ^m- represents an m-valent anion containing at least one element selected from the group consisting of W, Mo, Si, and P and oxygen. m represents any natural number.

In the formula (AIX), R ⁴¹ to R ⁴⁴ independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbons, an alkyl group having 2 to 20 carbons, which may have a substituent, and the methylene group constituting the alkyl group is inserted between Groups with oxygen atoms (but multiple oxygen atoms will not be inserted adjacently), monovalent aromatic hydrocarbon groups with 6 to 14 carbons that may have substituents, and aralkyls with 7 to 11 carbons that may have substituents Radical or hydrogen atom. R ⁴¹ and R ⁴² may be bonded to form a ring together with the bonded nitrogen atoms, and R ⁴³ and R ⁴⁴ may be bonded to form a ring together with the bonded nitrogen atoms.

R ⁴⁷ to R ⁵⁴ independently represent a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbons, when the carbon number is 2 or more, Oxygen atoms may be inserted between the methylene groups constituting the alkyl group (but a plurality of oxygen atoms will not be inserted adjacently). R ⁴⁸ and R ^{52 are} bonded to each other to form -NH-, -O-, -S- or -SO ₂ -.

T ¹ represents a monovalent aromatic heterocyclic group which may have a substituent.

When m is a natural number of 2 or more, a plurality of X ⁺ may have the same structure or different structures.

Examples of monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms represented by R ⁴¹ to R ⁴⁴ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. Straight-chain alkyl groups having 1 to 20 carbons such as hexadecyl, dodecyl, hexadecyl, and eicosyl; isopropyl, isobutyl, second butyl, third butyl, isoamyl Branched chain alkyl groups with 3 to 20 carbon atoms such as cyclopropyl, neopentyl and 2-ethylhexyl; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and tricyclodecyl, etc. Alicyclic saturated hydrocarbon groups with 3 to 20 carbon atoms, etc. It is preferably a linear or branched chain alkyl group with 1 to 12 carbons, more preferably a linear or branched chain alkyl group with 1 to 8 carbons, and even more preferably a linear chain with 1 to 6 carbons Or branched chain alkyl.

Substituents that may be possessed by the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, such as halogen atoms (fluorine atom, chlorine atom, bromine atom or iodine atom), cyano group, nitro group, hydroxyl group, substituted or unsubstituted amine group, etc. .

Regarding R ⁴¹ to R ⁴⁴ , an alkyl group having 2 to 20 carbon atoms and a group having an oxygen atom inserted between the methylene groups constituting the alkyl group, for example, -CH ₂ -O-CH ₃ group, -CH ₂ -O-CH _2- CH ₃ group, -CH ₂ -CH ₂ -O-CH ₂ -CH ₃ group, etc. Examples of alkyl groups having 2 to 20 carbon atoms include ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and eicosane Straight-chain alkyl with 2 to 20 carbons such as the group; the carbon number of isopropyl, isobutyl, 2nd butyl, 3rd butyl, isopentyl, neopentyl and 2-ethylhexyl, etc. 3 to 20 branched chain alkyl. More preferably, it is a linear or branched alkyl group having 2 to 12 carbons, more preferably is a linear or branched chain alkyl group having 2 to 8 carbons, and even more preferably a linear or branched chain alkyl group having 2 to 6 carbons. Or branched chain alkyl.

Examples of the monovalent aromatic hydrocarbon groups having 6 to 14 carbon atoms represented by R ⁴¹ to R ⁴⁴ include phenyl, tolyl, xylyl, mesityl, propylphenyl, butylphenyl, naphthyl, and the like. As a substituent that a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms may have, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), a cyano group, a nitro group, a hydroxyl group, an alkoxy group, and a carbon number of 1 To 8 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted amine, and the like.

As ^{the aralkyl group having 7 to 11 carbon atoms represented by R 41} to R ⁴⁴ , for example, benzyl, phenethyl, phenylpropyl, 2-methylphenylmethyl, 3-methylphenylmethyl, 4 -Methylphenylmethyl, 2,3-dimethylphenylmethyl, 2,4-dimethylphenylmethyl, 2,5-dimethylphenylmethyl, 2,6-dimethyl Phenylmethyl, 3,4-dimethylphenylmethyl, naphthylmethyl, etc.

As a substituent that the aralkyl group having 7 to 11 carbon atoms may have, for example, halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom), cyano group, nitro group, hydroxyl group, alkoxy group, substituted or unsubstituted Amine group and so on.

As a ring in which R ⁴¹ and R ^{42 are} bonded and can be formed together with the bonded nitrogen atoms, R ⁴³ and R ^{44 are} bonded and can be formed together with the bonded nitrogen atoms, such as a pyrrole ring , Pyrrolidine ring, piperidine ring, imidazole ring, indole ring, purine ring, ethyleneimine ring, 1H-azetidine ring, azetidine ring, hexamethyleneimine ring, aza Heptatriene ring, imidazoline ring, morpholine ring, thiazine ring, carbazole ring, etc.

Among them, R ⁴¹ to R ^{44 are} each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

Examples of the alkyl groups having 1 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl; Branched chain alkyl groups such as butyl group, isobutyl group, 2nd butyl group, 3rd butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group. It is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, and a butyl group.

Regarding R ⁴⁷ to R ⁵⁴ , the alkyl group having an oxygen atom inserted between the methylene groups constituting the alkyl group is an alkyl group having 2 to 8 carbon atoms and an oxygen atom is inserted between the methylene groups constituting the alkyl group, for example- CH ₂ -O-CH ₃ group, -CH ₂ -O-CH ₂ -CH ₃ group, -CH ₂ -CH ₂ -O-CH ₂ -CH ₃ group, etc.

Among them, R ⁴⁷ to R ^{54 are} each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Regarding T ¹ , the aromatic heterocyclic group constituting the monovalent aromatic heterocyclic group may be any of monocyclic or polycyclic, such as pyrrole, furan, thiophene, imidazole, pyrazole, oxazole, and isoxazole , Thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, 1,2,3-triazine (trazine), quinoline, isoquinoline, quinazoline , Indole, benzimidazole, benzofuran, purine, acridine, phenoxazine, phenothiazine, etc.

As the substituent that the aromatic heterocyclic group may have, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), a cyano group, a nitro group, a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, and a carbon number of 1 To 8 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted amine, and the like.

[Y] ^m- represents an m-valent anion containing at least one element selected from the group consisting of W, Mo, Si, and P and oxygen. m represents any natural number.

From the viewpoints of solvent resistance, heat resistance, etc., the anion is preferably the above-mentioned polyacid, and more preferable specific examples are as described above. m is preferably a natural number from 1 to 10, and more preferably a natural number from 1 to 6.

[1-2] Dyes

The colorant (A) may contain dyes in addition to lake pigments.

The dye is not particularly limited, and conventional dyes such as solvent dyes, acid dyes, direct dyes, and mordant dyes can be used. As dyes, for example, in the color index (published by The Society of Dyers and Colorists), pigments are classified into compounds having hue, and conventional dyes described in the dyeing notes (color dyeing company) other than pigments. Moreover, according to the chemical structure, for example, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes Based dyes, methine azo dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes. Among them, organic solvents Soluble dyes are ideal.

Specifically, for example, CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189; CI Solvent Red 45, 49, 111 , 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; CI solvent orange 2, 7, 11, 15, 26, 56, 77, 86; CI solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI solvent blue 4, 5, 14, 18, 35, 36, 37, 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, 128, 132, 136, 139; CI solvent dyes such as CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35; CI acid yellow 1 , 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114 , 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193 , 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426; CI acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64 , 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102; 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, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340; CI Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50: 1, 58, 63, 65, 80 CI acid dyes such as, 104, 105, 106, 109; CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93 , 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; CI direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; CI direct orange 26 , 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI direct purple 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI direct blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40 , 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106 , 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167 , 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214 , 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274 , 275, 293; CI direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. CI direct dyes; CI disperse yellow 51, 54 , 76; CI disperse violet 26, 27; CI disperse blue 1, 14, 56, 60 and other CI disperse dyes; CI basic red 1, 10; 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 base Violet 2; CI Basic Red 9; CI Basic Dyes such as CI Basic Green 1; CI Reactive Yellow 2, 76, 116; CI Reactive Orange 16; CI Reactive Dyes such as CI Reactive Red 36; CI Mordant Yellow 5 , 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI mordant red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95; CI mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI Mordant Violet 1, 1: 1, 2, 3, 4, 5, 6, 7, 8 , 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45 , 47, 48, 49, 53, 58; CI 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; CI mordant green 1, 3, 4, 5, 10, 13, 15, 19, 21 , 23, 26, 29, 31, 33, 34, 35, 41, 43, 53 and other CI mordant dyes, CI vat green 1 and other CI vat dyes.

These dyes can be appropriately selected according to the spectroscopic spectrum of the desired color filter.

Among them, in the case of using a dye, it is preferable that the dye contains a dibenzopyran dye from the viewpoint of solvent resistance, heat resistance, etc., and from the viewpoint of obtaining good brightness.

Dibenzopyran dye is a dye containing a compound with a dibenzopyran skeleton in the molecule. As dibenzopyran dyes, for example, CI Acid Red 51, 52, 87, 92, 94, 289, 388; CI Acid Violet 9, 30, 102; CI Basic Red 1 (Rose Red 6G), 2, 3, 4, 8; CI Basic Red 10, 11; CI Basic Violet 10 (Rose Red B), 11; CI Solvent Red 218; CI Mordant Red 27; CI Reactive Red 36 (Rose Bengal B); Sulfo-Rose Red B; Dibenzopyran dye described in JP 2010-32999 A Materials and the dibenzopiperan dyes described in Patent No. 4492760. Among them, those dissolved in organic solvents are more desirable.

Among these, as the dibenzopiperan dye, a dye containing a compound represented by the formula (1a) (hereinafter referred to as a compound (1a) in some cases) is more preferable.

Compound (1a) may be its tautomer. In the case of further including the dibenzopiperan dye as the colorant (A), the content ratio of the compound (1a) in the dibenzopiperan dye is more preferably 50% by mass or more, and more preferably 70% by mass or more, More preferably, it is 90% by mass or more. As the dibenzopyran dye, it is preferable to use only the compound (1a).

In the formula (1a), R ¹ to R ⁴ independently represent a hydrogen atom, an optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbons, and an optionally substituted monovalent aralkyl group having 7 to 20 carbons Or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and the saturated hydrocarbon group and the -CH ₂ -contained in the aralkyl group may be substituted by -O-, -CO- or -NR ^11- . R ¹ and R ² may together form a ring containing a nitrogen atom, and R ³ and R ⁴ may together form a ring containing a nitrogen atom.

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

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

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

a represents an integer of 0 or 1.

X represents a halogen atom.

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

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

R ⁹ and R ¹⁰ independently represent a hydrogen atom or an optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbons. The -CH ₂ -contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, -NH- or -NR ⁸ -substituted, R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom.

R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbons, or an aralkyl group having 7 to 10 carbons. In the formula (1a), when -SO ₃ ^- exists, the number is one.

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

Examples of the aromatic hydrocarbon group may have a substituent such as a halogen atom, which may be substituted with a halogen atom having 1 to 20 monovalent saturated hydrocarbon _{^{group, -OH, -OR 8, -SO 3}} -, -SO 3 H, - SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ . Among these, as a substituent group, is desirable as ^{_{-SO 3 -, -SO 3 H,}} -SO 3 - Z + and -SO ₂ NR ⁹ R ^10, more preferably of -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ . In this case, -SO ₃ ^- Z ⁺ is preferably -SO ₃ ^-+ N(R ¹¹ ) ₄ . When R ¹ to R ⁴ are these groups, the colored curable resin composition of the present invention containing the compound (1a) can form a color filter with less foreign matter generation and better solvent resistance and heat resistance.

As a ^{monovalent saturated hydrocarbon group of 1 to 20 carbons from R 1} to R ⁴ and R ⁸ to R ¹¹ , for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl Straight-chain alkyl such as, decyl, dodecyl, hexadecyl, eicosyl, etc.; branches of isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl, etc. Chain alkyl; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl and other alicyclic saturated hydrocarbon groups with 3 to 20 carbons, etc.

The hydrogen atoms contained in the saturated hydrocarbon groups R ¹ to R ⁴ may be substituted by halogen atoms, for example.

As ^{the aralkyl group represented by R 1} to R ⁴ , for example, the same example as the aralkyl group represented by R ⁴¹ to R ⁴⁴ .

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

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

As -OR ⁸ , for example, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and eicosanoxy Base and so on.

Examples of -CO ₂ R ⁸ include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, 3rd butoxycarbonyl, hexyloxycarbonyl, and eicosyloxycarbonyl.

Examples of -SR ⁸ include methylsulfanyl, ethylsulfanyl, butylsulfanyl, hexylsulfanyl, decylsulfanyl, and eicosylsulfanyl.

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

As -SO ₃ R ⁸ , for example, methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, 3rd butoxysulfonyl, hexyloxysulfonyl and eicosanyloxy Sulfonyl.

As -SO ₂ NR ⁹ R ¹⁰ , for example, sulfasulfonyl; N-methylsulfasulfonyl, N-ethylsulfasulfonyl, N-propylsulfasulfonyl, N-isopropylsulfasulfonyl Group, N-butylsulfasulfonyl, N-isobutylsulfasulfonyl, N-second butylsulfasulfonyl, N-third butylsulfasulfonyl, N-pentylsulfasulfonyl Group, N-(1-ethylpropyl)sulfasulfonyl, N-(1,1-dimethylpropyl)sulfasulfonyl, N-(1,2-dimethylpropyl)sulfasulfon Amino, N-(2,2-dimethylpropyl)sulfasulfonyl, N-(1-methylbutyl)sulfasulfonyl, N-(2-methylbutyl)sulfasulfonyl , N-(3-Methylbutyl)sulfasulfonyl, N-cyclopentylsulfasulfonyl, N-hexylsulfasulfonyl, N-(1,3-dimethylbutyl)sulfasulfonyl Group, N-(3,3-dimethylbutyl)sulfasulfonyl, N-heptylsulfasulfonyl, N-(1-methylhexyl)sulfasulfonyl, N-(1,4- Dimethylpentyl)sulfasulfonyl, N-octylsulfasulfonyl, N-(2-ethylhexyl)sulfasulfonyl, N-(1,5-dimethyl)hexylsulfasulfonyl , N-(1,1,2,2-tetramethylbutyl)sulfasulfonyl and other N-1 substituted sulfasulfonyl groups; N,N-dimethylsulfasulfonyl, N,N-ethyl Methylsulfamate, N,N-diethylsulfamate, N,N-propylmethylsulfamate, N,N-isopropylmethylsulfamate, N,N -3rd butyl methyl sulfasulfonyl, N,N-butyl ethyl sulfasulfonyl, N,N-bis(1-methylpropyl) sulfasulfonyl, N,N-heptyl methylamine N, N-2 substituted sulfamoyl groups such as sulfonyl groups and the like.

In R ^{5 _{-CO 2 H, -CO 2 - Z}} +, -CO 2 R 8, -SO 3 -, -SO 3 - Z +, -SO 3 H or SO ₂ NHR ⁹ is desirable, -SO ₃ ^-, -SO ₃ ^- Z ⁺ , -SO ₃ H or SO ₂ NHR ^{9 are} more desirable.

It is preferable that m is 1 to 4, and 1 or 2 is more preferable.

Examples of the alkyl groups having 1 to 6 carbon atoms in R ⁶ and R ⁷ include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.; isopropyl, isobutyl, isopropyl Branched chain alkyl groups such as pentyl and neopentyl.

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

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

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

The compound (1a) is preferably a compound represented by formula (2a) (hereinafter, it may be referred to as "compound (2a)"). Compound (2a) may be its tautomer.

In the formula (2a), R ²¹ to R ²⁴ independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbons, or an optionally substituted monovalent aromatic hydrocarbon group having 6 to 10 carbons. R ²¹ and R ²² together can form a ring containing a nitrogen atom, and R ²³ and R ²⁴ can together form a ring containing a nitrogen atom.

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

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

a1 represents an integer of 0 or 1.

X1 represents a halogen atom.

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

Z ⁺ represents ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , four R ²⁷ , which may be the same or different.

R ²⁷ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group.

In the formula (2a), the monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms of ^{R 21} to R ^{24 are} , for example, the same groups exemplified as the aforementioned aromatic hydrocarbon groups of ^{R 1} to R ^4.

The hydrogen atom contained in an aromatic hydrocarbon, may be ^{_{-SO 3 -, -SO 3 H,}} -SO 3 - Z1 +, -SO 3 R 26 or -SO ₂ NHR ²⁶ group.

In formula (2a), R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon groups are replaced by -SO ₃ ^- ,- The groups substituted with SO ₃ H, -SO ₃ ^- Z1 ⁺ , -SO ₃ R ²⁶ or -SO ₂ NHR ^{26 are preferable.}

More preferably, R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon groups are -SO ₃ ^- Z1 ⁺ or -SO ₂ NHR ²⁶ substituted group.

When R ²¹ to R ²⁴ are these groups, the coloring curable resin composition of the present invention containing the compound (2a) can form a color filter having better solvent resistance and heat resistance.

As ^{the ring containing a nitrogen atom formed by R 21} and R ²² together and the ring containing a nitrogen atom formed by R ³ and R ⁴ together, for example, the ring formed together ^{with R 1} and R ^{2 is the same ring.} Among them, aliphatic heterocycles are more desirable. As this aliphatic heterocyclic ring, the following ring is mentioned, for example.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms of R ²¹ to R ²⁴ , R ²⁶ and R ^{27 are} the same as those exemplified as the saturated hydrocarbon group of ^{R 8} to R ^11.

The saturated hydrocarbon groups represented by R ²¹ to R ^{24 are} preferably each independently a methyl group or an ethyl group.

As a -SO ₃ R ²⁶ and -SO ₂ NHR R ²⁶ of ^26, than over the branched chain alkyl group having a carbon number of 3 to 20, more preferably branched chain alkyl group having a carbon number of 6 to 12, more desirably 2 -Ethylhexyl. When R ^{26 is} such a group, the coloring curable resin composition of the present invention containing the compound (2a) can form a color filter having better solvent resistance and heat resistance.

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

As the aforementioned ⁺ N(R ²⁷ ) ₄ , it ^{is preferable that at least two of the four R 27} are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. Further, R 4 to ²⁷ total carbon number of 20 to 80 is desirable, more preferably to 20 to 60. ^{When +} N(R ²⁷ ) ₄ is present in the compound (2a) and R ^{27 is} such a group, the colored curable resin composition of the present invention containing the compound (2a) can provide solvent resistance and heat resistance Better color filters.

It is more desirable for m1 to be 1 to 4, and 1 or 2 is more desirable.

The compound (1a) is preferably a compound represented by formula (3a) (hereinafter, it may be referred to as "compound (3a)"). Compound (3a) may be its tautomer.

In the formula (3a), R ³¹ and R ³² independently represent a monovalent saturated hydrocarbon group with 1 to 10 carbons or a monovalent aralkyl group with 7 to 10 carbons, and the saturated hydrocarbon group and the aralkyl group contained The hydrogen atoms may be substituted by halogen atoms, and the hydrogen atoms contained in the aromatic hydrocarbon group of the aralkyl group may be substituted by an alkoxy group having 1 to 3 carbon atoms. The saturated hydrocarbon group and the aralkyl group contained The -CH ₂ -can be replaced by -O-, -CO- or -NR ¹¹ -.

R ³³ and R ³⁴ independently represent an alkyl group having 1 to 4 carbons, an alkylsulfonyl group having 1 to 4 carbons, or an alkylsulfonyl group having 1 to 4 carbons.

R ³¹ and R ³³ together can form a ring containing a nitrogen atom, and R ³² and R ³⁴ together can form a ring containing a nitrogen atom.

p and q each independently represent an integer from 0 to 5. When p is 2 or more, the plurality of R ³³ may be the same or different, and when q is 2 or more, the plurality of R ³⁴ may be the same or different.

R ¹¹ represents the same meaning as described above.

Examples of the monovalent saturated hydrocarbon groups having 1 to 10 carbon atoms in R ³¹ and R ^{32 include} linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl; Branched chain alkyl such as propyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl, etc.; carbon number of cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. 3 to 10 alicyclic saturated hydrocarbon groups.

Examples of the aralkyl group for R ³¹ and R ³² include phenylene and the like.

As the alkoxy group having 1 to 3 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group and the like.

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

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

As R ³³ and R ³⁴ , the alkyl sulfhydryl group having 1 to 4 carbon atoms, such as methylsulfhydryl, ethylsulfhydryl, propylsulfhydryl, butylsulfhydryl, and isopropylsulfhydryl Wait.

Examples of R ³³ and R ³⁴ include alkylsulfonyl groups having 1 to 4 carbon atoms, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl and isopropylsulfonyl Wait.

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

It is preferable that p and q are integers from 0 to 2, and 0 or 1 is more preferable.

As the compound (1a), for example, compounds represented by formula (1-1) to formula (1-43). Furthermore, in the formula, R ⁴⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbons, more preferably a branched chain alkyl group having 6 to 12 carbons, and more preferably 2-ethylhexyl.

Among the above compounds, the compounds represented by formula (1-1) to formula (1-23) or formula (1-37) to formula (1-43) correspond to compound (2a), formula (1-24) to formula The compound represented by any one of (1-36) corresponds to the compound (3a).

Among them, the sulfonamide of C.I. Acid Red 289, the quaternary ammonium salt of C.I. Acid Red 289, the sulfonamide of C.I. Acid Violet 102, or the quaternary ammonium salt of C.I. Acid Violet 102 are more desirable. As such a compound, for example, a compound represented by (1-1) to formula (1-8), formula (1-11), or formula (1-12), and the like.

Furthermore, at the point of good solubility in organic solvents, a compound represented by any one of (1-24) to formula (1-33) is preferable.

For dibenzopiperan dyes, commercially available dibenzopiperan dyes can be used (for example, "Chugai Aminol Fast Pink RH/C" manufactured by Chugai Chemical Co., Ltd., and "Rodamin 6G" manufactured by Taoka Chemical Industry Co., Ltd.) . In addition, commercially available dibenzopyran dyes can be used as starting materials and can also be synthesized with reference to Japanese Patent Application Laid-Open No. 2010-32999.

[1-3] Coloring Pigments

The coloring agent (A), in addition to lake pigments, may further contain coloring pigments (but different from lake pigments). The coloring pigment is not particularly limited, and conventional coloring pigments can be used, for example, pigments classified as pigments in the color index (published by The Society of Dyers and Colorists).

As coloring pigments, for example, 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, etc. Orange pigment; 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 Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60, etc.; CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple 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; etc.

As the coloring pigment, CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other blue pigments are preferred. The pigments are more ideally CI Pigment Blue 15:3, 15:6 and CI Pigment Violet 23, and more ideally CI Pigment Blue 15:6. By including the aforementioned coloring pigment, the transmission spectrum is easily optimized, and the light resistance and solvent resistance of the color filter become better.

Coloring pigments, if necessary, can be treated with rosin, surface treatment using pigment derivatives introduced with acidic or basic groups, grafting treatment of the pigment surface by polymer compounds, etc., by sulfuric acid micronization method, etc. Micronization treatment, or cleaning treatment with organic solvents, water, etc. in order to remove impurities, removal of ionic impurities by ion exchange method, etc. Processing etc.

It is desirable that the particle size of the colored pigment is uniform. When the pigment dispersant is contained and the dispersion treatment is performed, a pigment dispersant in which the color pigment is uniformly dispersed in the solution can be obtained.

Examples of the aforementioned pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, and other surfactants. These pigment dispersants can be used alone or in combination of two or more kinds. As a pigment dispersant, trade names such as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOREN (manufactured by Kyoeisha Chemical Co., Ltd.), SOLSPERSE (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA), Ajisper (Manufactured by Ajinomoto Fine Technology Co., Ltd.), Disperbyk (manufactured by BYK-Chemie), etc.

In the case of using a pigment dispersant, the amount used is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass and 50% by mass, based on the total amount of the color pigment. When the amount of the pigment dispersant used is in the aforementioned range, there is a tendency to obtain a pigment dispersion in a uniformly dispersed state.

[1-4] Content ratio of colorant (A)

The content ratio of the coloring agent (A) is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and even more preferably 10 to 50% by mass based on the total solid content of the colored curable resin composition %. When the content ratio of the colorant (A) is within the aforementioned range, the color density when it becomes a color filter is sufficient, and the composition can contain the required amount of resin (B) and polymerizable compound (C), which can provide mechanical strength Full graphics. Here, the so-called The "total solid content" refers to the total amount of the colored curable resin composition excluding the solvent content. The total amount of solid components and the content ratio of each component to it can be measured by conventional analytical means such as liquid chromatography or gas chromatography, for example.

From the viewpoint of solvent resistance and heat resistance, the content ratio of the lake pigment of the colorant (A) is preferably 2.5 to 100% by mass, and more preferably 45 to 100 in 100% by mass of the colorant (A). The mass% is more preferably 75 to 100% by mass, and particularly preferably 90 to 100% by mass.

When the colorant (A) contains a dye, from the viewpoints of solvent resistance and heat resistance, the content of the dye in the colorant (A) is usually 0.1 to 98% by mass in 100% by mass of the colorant (A) , More desirably 0.1 to 60 mass%, more desirably 0.1 to 50 mass%, still more desirably 0.5 to 25 mass%, particularly desirably 0.5 to 10 mass%.

When the coloring agent (A) contains a coloring pigment, from the viewpoint of solvent resistance and heat resistance, the content of the coloring pigment of the coloring agent (A) is usually 0.1 to 98 in 100% by mass of the coloring agent (A) The mass% is preferably 0.1 to 60 mass%, more preferably 0.1 to 50 mass%, still more preferably 0.5 to 25 mass%, particularly preferably 0.5 to 10 mass%.

[2] Resin (B)

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. As the resin (B), for example, the following resins [K1] to [K6] and the like.

Resin [K1]; at least one selected from the group of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter referred to as "(a)") and having carbon Copolymer of 2 to 4 cyclic ether structure and ethylenically unsaturated bond monomer (b) (hereinafter referred to as "(b)"); resin [K2]; (a), (b) ) And (a) copolymerizable monomer (c) (but different from (a) and (b)) (hereinafter referred to as "(c)") copolymer; resin [K3]; ( a) Copolymer with (c); Resin [K4]; Copolymer with (a) and (c), Resin that reacts with (b); Resin [K5]; Copolymer with (b) and (c) Substance, the resin reacted with (a); resin [K6]; the copolymer of (b) and (c), reacted with (a), and then reacted with carboxylic anhydride.

As (a), for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid; maleic acid, fumaric acid, pyromellitic acid Acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid , 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid and other unsaturated dicarboxylic acids; methyl-5-norcamphor Ene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methyl Bicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2 -Alkenes, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other carboxyl-containing bicyclic unsaturated compounds; Maleic anhydride, fumaric anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride Acid anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. Saturated dicarboxylic acid anhydride; succinic acid mono[2-(meth)acryloyloxyethyl] ester, phthalic acid mono[2-(meth)acryloyloxyethyl] ester, etc. Unsaturated mono[(meth)acryloyloxyalkyl] esters of polycarboxylic acids; such as α-(hydroxymeth)acrylic acid and other unsaturated acrylates containing hydroxyl and carboxyl groups in the same molecule; etc.

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

(b) It is a cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and polymerization of ethylenically unsaturated bonds Sexual compounds. (b) A monomer having a cyclic ether having a carbon number of 2 to 4 and a (meth)acryloxy group is preferable.

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

As (b), for example, a monomer (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter referred to as "(b1)"), and a monomer having an oxetanyl group and an ethylenically unsaturated bond Monomer (b2) (hereinafter referred to as "(b2)" Case), monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter referred to as "(b3)" in some cases), etc.

As (b1), for example, a linear or branched aliphatic unsaturated hydrocarbon monomer (b1-1) having an epoxy-based structure (hereinafter referred to as "(b1-1)"), The alicyclic unsaturated hydrocarbon has a monomer (b1-2) (hereinafter referred to as "(b1-2)") having an epoxy-based structure, and the like.

As (b1-1), for example, glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl Vinyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o- Vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α-methyl-p-vinyl benzyl glycidyl ether, 2,3 -Bis(glycidoxymethyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2, 6-bis(glycidoxymethyl)styrene, 2,3,4-tris(glycidoxymethyl)styrene, 2,3,5-tris(glycidoxymethyl) Styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris(glycidoxymethyl)styrene, 2,4,6-tris(cyclo Oxypropoxymethyl) styrene and the like.

As (b1-2), for example, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE2000; manufactured by DAICEL Co., Ltd.), (meth)acrylic acid 3, 4-epoxycyclohexyl methyl ester (for example, CYCLOMER A400; manufactured by DAICEL (stock)), 3,4-epoxycyclohexyl methyl (meth)acrylate (for example, CYCLOMER M100; manufactured by DAICEL (stock)), formula The compound represented by (I) and the compound represented by formula (II), etc.

[In the formula (I) and Formula (II), R ^a and R ^b represents a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, the hydrogen atoms contained in the alkyl group may be substituted with hydroxy.

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

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

* Indicates the bonding bond with O. ]

As the alkyl group having 1 to 4 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2nd butyl, 3rd butyl and the like.

Examples of alkyl groups in which a hydrogen atom is substituted with a hydroxy group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1 -Methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc.

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

As the alkanediyl group, for example, methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl Base, hexane-1,6-diyl, etc.

X ^a and X ^b are preferably, for example, a single bond, methylene, ethylene, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, and more preferably, for example, a single bond, * -CH ₂ CH ₂ -O- (* indicates the bonding bond with O).

As the compound represented by formula (I), for example, formula (I-1) to (I-15) Any one of the compounds and so on. Among them, the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9) or the formula (I-11) to the formula (I The compound represented by -15) is more preferably a compound represented by formula (I-1), formula (I-7), formula (I-9), or formula (I-15).

As the compound represented by the formula (II), for example, a compound represented by any one of the formulas (II-1) to (II-15), and the like. Among them, the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II-9) or the formula (II-11) to the formula (II) are more ideal The compound represented by -15) is more preferably a compound represented by formula (II-1), formula (II-7), formula (II-9), or formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone, respectively, or two or more of them may be used in combination. When the compound represented by formula (I) and the compound represented by formula (II) are used in combination, the content ratio [compound represented by formula (I): compound represented by formula (II)] is preferably based on moles It is 5:95 to 95:5, more preferably 20:80 to 80:20.

As (b2), it is more preferable that it is a monomer which has an oxetanyl group and a (meth)acryloxy group. As (b2), for example, 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-methacryloyloxymethyloxetane Butane, 3-ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-methyl-3- Methacryloxyethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, 3-ethyl-3-methacryloxyethyl oxetane Cyclobutane, 3-ethyl-3-propenyloxyethyloxetane and the like.

As (b3), it is more preferable that it is a monomer which has a tetrahydrofuran group and a (meth)acryloxy group. Specific examples of (b3) include methyl tetrahydrofuran acrylate (for example, BISCOAT V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), methyl tetrahydrofuran methacrylate, and the like.

As (b), since the reliability of heat resistance, chemical resistance, etc. of the obtained color filter can be improved more, (b1) is more preferable. Furthermore, it is more desirable to be (b1-2) at the point of good storage stability of the colored curable resin composition.

As (c), for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2 butyl (meth) acrylate, 3 butyl (meth) acrylate , 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, ( Cyclohexyl meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-(meth)acrylate (common name in this technical field is " (Meth) dicyclopentyl acrylate". Also called "tricyclodecyl (meth)acrylate"), (meth)acrylate tricyclo[5.2.1.0 ^2,6 ]decene-8 -Esters (commonly known in the technical field as "dicyclopentenyl (meth)acrylate". Also called "tricyclodecenyl (meth)acrylate"), (meth)acrylic acid bicyclic Pentoxyethyl, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propynyl (meth)acrylate, phenyl (meth)acrylate, (Meth)acrylates such as naphthyl (meth)acrylate and benzyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. containing hydroxyl groups (Meth) acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxy Methylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2 -Ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[ 2.2.1]Hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept -2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5 -Ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-th3 butoxycarbonylbicyclo[2.2.1 ]Hept-2-ene, 5-cyclohexoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis( The 3rd butoxycarbonyl) bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexoxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N -Phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide Amine, N-succinimidyl-3-maleimidin benzoate, N-succinimidyl-4-maleimidin butyrate, N-succinimidyl-6 -Dicarbonyl imines such as maleimide caproate, N-succinimidyl-3-maleimide propionate, N-(9-acridinyl) maleimide, etc. Derivatives; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, Vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene; etc.

Among them, styrene, vinyl toluene, N-benzyl maleimide, N-cyclohexyl maleimide, and N-benzene are preferred in terms of copolymerization reactivity and heat resistance. Methyl maleimide, bicyclo[2.2.1]hept-2-ene, etc.

For resin [K1], the ratio from each structural unit, among all the structural units constituting resin [K1],

Building unit from (a); 2 to 60 mol%

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

More ideal,

Building unit from (a); 10 to 50 mol%

Building unit from (b); 50 to 90 mol%

More ideal.

When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability of the colored curable resin composition, the developability when a colored pattern is formed, and the solvent resistance of the resulting color filter tend to be good.

Resin [K1], for example, please refer to the literature "Synthetic polymer Experimental method" (Otsu Takayuki, Publishing House (Stock) Chemical Doujin, 1st Edition, 1st Brush, Issued on March 1, 1972) and the production of the cited documents recorded in this document.

Specifically, for example, the predetermined amounts of (a) and (b), polymerization initiator, solvent, etc. are put into the reaction vessel, for example, by replacing oxygen with nitrogen, heating and keeping warm while stirring in a deoxygenated environment. Furthermore, the polymerization initiator and solvent used here are not particularly limited, and ordinary users in this field can be used. For example, as a polymerization initiator, for example, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), organic peroxides (Benzyl peroxide etc.) As the solvent, it is sufficient if it can dissolve each monomer, for example, the solvent which is the solvent (E) of the coloring curable resin composition of the present invention will be described later.

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

For resin [K2], the ratio from each structural unit, among all the structural units constituting resin [K2],

Building unit from (a); 2 to 45 mol%

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

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

More ideal,

Building unit from (a); 5 to 40 mol%

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

Building unit from (c); 5 to 60 mol%

More ideal.

When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance, heat resistance, and Tendency to have good mechanical strength.

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

For resin [K3], the ratio from each structural unit, among all the structural units constituting resin [K3],

Building unit from (a); 2 to 60 mol%

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

More ideal,

Building unit from (a); 10 to 50 mol%

Building unit from (c); 50 to 90 mol%

More ideal.

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

Resin [K4] can be obtained by obtaining a copolymer of (a) and (c), and adding the cyclic ether with a carbon number of 2 to 4 in (b) to the carboxylic acid and/ Or carboxylic acid anhydride.

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

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

Following the manufacture of the copolymer of (a) and (c), the atmosphere in the flask is replaced by nitrogen gas, and the reaction catalyst of (b), carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris(dimethylaminomethyl) Base) phenol, etc.) and polymerization inhibitors (hydroquinone, etc.) are placed in a flask, and the resin [K4] can be produced by reacting, for example, at 60 to 130°C for 1 to 10 hours.

The usage amount of (b) is preferably 5 to 80 mol, and more preferably 10 to 75 mol for (a) 100 mol. With this range, the storage stability of the colored curable resin composition, the developability during pattern formation, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting color filter tend to be better balanced. . Since the cyclic ether has high reactivity and is unlikely to remain unreacted (b), (b) used in the resin [K4] is preferably (b1), and more preferably (b1-1).

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

The reaction conditions such as the feeding method, reaction temperature, and time can be appropriately adjusted in consideration of manufacturing equipment, heat generation due to polymerization, and the like. Furthermore, as with the polymerization conditions, manufacturing equipment and development due to polymerization can be considered. The feeding method and reaction temperature are appropriately adjusted by heat and the like.

The resin [K5], as the first stage, is the same as the above-mentioned resin [K1] production method to obtain a copolymer of (b) and (c). In the same manner as above, the obtained copolymer may be used as it is after the reaction, a concentrated or diluted solution, or a solid (powder) obtained by reprecipitation or the like may be used.

The ratio of the structural units from (b) and (c), in terms of the total number of moles of all the structural units constituting the aforementioned copolymer, respectively

Building unit from (b); 5 to 95 mol%

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

More ideal,

Building unit from (b); 10 to 90 mol%

Building unit from (c); 10 to 90 mol%

More ideal.

Furthermore, under the same conditions as the production method of the resin [K4], the cyclic ether derived from (b) contained in the copolymer of (b) and (c) is used to make the carboxylic acid contained in (a) And/or carboxylic anhydride reaction can obtain resin [K5].

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

Resin [K6] is a resin in which resin [K5] reacts with carboxylic anhydride. The hydroxyl group produced by the reaction of the cyclic ether with the carboxylic acid or carboxylic anhydride reacts with the carboxylic anhydride.

As the carboxylic anhydride, for example, maleic anhydride, citraconic acid, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6 -Tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]heptan- 2-alkene anhydride and so on. The amount of carboxylic anhydride used is preferably 0.5 to 1 mol with respect to 1 mol of the amount of (a) used.

As the resin (B), specifically, for example, 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxy tricyclic acrylate [5.2.1.0 ^{2, 6} ] Resins such as decyl ester/(meth)acrylic acid copolymer [K1]; (meth)glycidyl acrylate/(meth)acrylic acid benzyl/(meth)acrylic acid copolymer, (meth) Glycidyl acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexyl maleate Resins such as imine copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer [K2]; (meth) Resins such as benzyl acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer, etc. [K3]; use (former) in benzyl(meth)acrylate/(meth)acrylic acid copolymer Base) glycidyl acrylate addition resin, (meth)acrylate tricyclodecyl ester/styrene/(meth)acrylic acid copolymer to (meth)acrylate glycidyl ester addition resin, in ( Resins such as tricyclodecyl methacrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer to add glycidyl (meth)acrylate [K4]; in (methyl) ) A copolymer of tricyclodecyl acrylate/glycidyl (meth)acrylate reacts with (meth)acrylic acid, and tricyclodecyl (meth)acrylate/styrene/(meth)acrylate epoxy The copolymer of propyl ester makes (meth)acrylic acid react with resin and other resins [K5]; in the copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate, (meth) Resins such as acrylic-reacted resins and resins such as tetrahydrophthalic anhydride-reacted resins [K6] and the like. Among them, as resin (B), resin [K1] and resin [K2] are more preferable.

The weight average molecular weight (Mw) of the resin (B) in terms of polystyrene is more preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. When the molecular weight is within the aforementioned range, the hardness of the color filter increases, the residual film rate is high, the unexposed portion has good solubility in the developing solution, and the resolution of the colored pattern tends to be improved.

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

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

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

[3] Polymerizable compound (C)

The polymerizable compound (C) is activated by the polymerization initiator (D) The compound which can be polymerized by a free radical and/or an acid, for example, a compound having a polymerizable ethylenic unsaturated bond, etc., is preferably a (meth)acrylate compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. As such a polymerizable compound, for example, trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, neopentylerythritol tetra(meth)acrylate, dineopentaerythritol Penta (meth) acrylate, dineopentyl hexa (meth) acrylate, trineopentaerythritol octa (meth) acrylate, trineopentaerythritol hepta (meth) acrylate, tetraneopentyl Tetraol deca(meth)acrylate, tetraneopentaerythritol nine(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, ethylene glycol modified new Pentylene erythritol tetra (meth) acrylate, ethylene glycol modified dineopentaerythritol hexa (meth) acrylate, propylene glycol modified neopentyl erythritol tetra (meth) acrylate, propylene glycol modified dineopentyl Tetraol hexa(meth)acrylate, caprolactone-modified neopentaerythritol tetra(meth)acrylate, caprolactone-modified dineopentaerythritol hexa(meth)acrylate, etc.

Among them, dineopentaerythritol penta(meth)acrylate and dineopentaerythritol hexa(meth)acrylate are more desirable.

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

The content ratio of the polymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, and even more preferably from 17 to 55 based on the total solid content of the colored curable resin composition. quality%. When the content ratio of the polymerizable compound (C) is within the aforementioned range, the residual film rate during the formation of the colored pattern and the solvent resistance of the color filter will be improved. Propensity.

[4] Polymerization initiator (D)

The polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization by generating active radicals, acids, etc. by the action of light and heat, and conventional polymerization initiators can be used. As a polymerization initiator that generates living radicals, for example, alkyl phenone compounds, triazine compounds, phosphine oxide compounds, O-oxime compounds, and bisimidazole compounds.

The aforementioned O-acetoxime compound is a compound having a structure represented by formula (d1). In the following, * represents a bonding key.

As the aforementioned O-anisyl oxime compound, for example, N-benzyloxy-1-(4-phenylhydrothiophenyl)butan-1-one-2-imine, N-benzyloxy -1-(4-phenylsulfanyl phenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)-3- Cyclopentylpropan-1-one-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-dioxa Cyclopentylmethyloxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2 -Methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyloxy-1-[9-ethyl-6-( 2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure OXE 01, OXE 02 (manufactured by BASF Co., Ltd. above), and N-1919 (manufactured by Adeka Co., Ltd.), etc. can also be used. Among them, O-acyl oxime The compound is preferably selected from N-benzyloxy-1-(4-phenylhydrothiophenyl)butan-1-one-2-imine, N-benzyloxy-1- (4-Phenylsulfanylsulfanylphenyl)octan-1-one-2-imine and N-benzyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentyl At least one of the groups of propane-1-one-2-imine, more preferably N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2 -Imines. In the case of these O-acetoxime compounds, there is a tendency to obtain a high-brightness color filter.

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

As the compound having the structure represented by the formula (d2), for example, 2-methyl-2-(N-morpholinyl)-1-(4-methylsulfanylphenyl)propan-1-one, 2-di Methylamino-1-(4-morpholinylphenyl)-2-benzylbutane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl) Methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. Commercial products such as Irgacure 369, 907, and 379 (manufactured by BASF (above)) can also be used.

As the compound having the structure represented by the formula (d3), for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl (Ethoxy) phenyl) propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl) propan-1-one oligomerization Substances, α,α-diethoxy acetophenone, benzyl dimethyl ketal, etc.

At the point of sensitivity, as an alkylphenone compound, it is more It is ideally a compound having a structure represented by formula (d2).

As the aforementioned triazine compound, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) )-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2 ,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2- (5-Methylfuran-2-yl)vinyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl ]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1, 3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

As the aforementioned phosphine oxide compound, for example, 2,4,6-trimethylbenzyldiphenylphosphine oxide and the like. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF Co., Ltd.) can also be used.

As the aforementioned bisimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,3-dichloro Phenyl)-4,4',5,5'-tetraphenylbisimidazole (refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'-bis(2-chloro Phenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxybenzene) Yl)bisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)bisimidazole, 2,2'-bis(2- Chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)bisimidazole (refer to Japanese Patent Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, etc.), 4 , Imidazole compounds in which the phenyl group at the 4', 5, and 5'-positions is substituted with a carbonyl alkoxy group (refer to Japanese Patent Application Laid-Open No. 7-10913 etc.) and the like.

Furthermore, as the polymerization initiator (D), for example, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, o-benzophenone Methyl benzoate, 4-phenylbenzophenone, 4-benzyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis (3rd butyl peroxide Carbonyl) benzophenone compounds such as benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone (phenanthrenequinone), 2-ethylanthraquinone, camphorquinone and other quinones Compounds; 10-butyl-2-chloroacridone, diphenylethylenedione, methyl phenylglyoxylate, titanocene compounds, etc. These are preferably used in combination with the polymerization initiator (D1) (especially an amine compound) described later.

As an acid generator, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethyl Sulfonium p-toluenesulfonate, 4-acetoxyphenyl‧methyl‧benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexa Onium salts such as fluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzoin tosylate, etc.

The polymerization initiator (D) is preferably a polymerization containing at least one selected from the group consisting of alkylphenone compounds, triazine compounds, phosphine oxide compounds, O-oxime compounds, and bisimidazole compounds The initiator is more preferably a polymerization initiator containing an O-acetoxime compound.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Content of polymerization initiator (D) When it is within the aforementioned range, the exposure time tends to be shortened due to increased sensitivity, so the productivity of the color filter is improved.

[5] Polymerization initiator (D1)

The colored curable resin composition of the present invention may contain a polymerization initiator (D1). The polymerization initiation auxiliary (D1) is a compound used to promote the polymerization of a polymerizable compound whose polymerization is initiated by a polymerization initiator, or a sensitizer. When the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D). Examples of the polymerization initiation auxiliary (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds, and the like.

As the aforementioned amine compound, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl ester, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylamine Benzoic acid isoamyl ester, benzoic acid 2-dimethylamino ethyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, N,N-dimethyl-p-toluidine, 4,4' -Bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamine) Among them, 4,4'-bis(diethylamino)benzophenone is preferable. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

As the aforementioned alkoxyanthracene compound, for example, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9 ,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

As the aforementioned thioxanthone compound, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone Ketones, 1-chloro-4-propoxythioxanthone, etc.

As the aforementioned carboxylic acid compound, for example, phenyl sulfanyl acetic acid, methyl phenyl sulfanyl acetic acid, ethyl phenyl sulfanyl acetic acid, methyl ethyl phenyl sulfanyl acetic acid, dimethyl phenyl sulfanil Glycolic acid, methoxyphenyl thioglycine, dimethoxyphenyl thioglycolic acid, chlorophenyl thioglycolic acid, dichlorophenyl thioglycolic acid, N-phenylglycine, benzene Oxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, etc.

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

[6] Extender Pigment (P)

The colored curable resin composition system of the present invention contains an extender pigment (P). According to the colored curable resin composition of the present invention containing the colorant (A) and the extender pigment (P), the solvent resistance and heat resistance of the cured film (color filter, etc.) can be improved.

The extender pigment (P) is not particularly limited, and conventional extender pigments can be used, such as zinc oxide (ZnO), titanium oxide (TiO ₂ ), silicon _{oxide (SiO 2} ), zirconium oxide (ZrO ₂ ), barium carbonate ( Extender pigments such as BaCO ₃ ), calcium carbonate (CaCO ₃ ), basic magnesium carbonate (MgCO ₃ ), aluminum hydroxide (Al(OH) ₃ ), kaolin, and Nepheline syenite.

Among them, from the viewpoints of solvent resistance and heat resistance, the extender pigment (P) is preferably selected from the group consisting of zinc oxide, titanium oxide, silicon oxide, zirconium oxide, barium carbonate, calcium carbonate, and basic magnesium carbonate At least one of, and more desirably at least one selected from the group consisting of zinc oxide, titanium oxide, silicon oxide, and zirconium oxide. Furthermore, in order to obtain a composition capable of producing a high-brightness color filter, among these, the one with high transparency is preferable. For the extender pigment (P), at the point of high transparency, the primary particle size is preferably 0.1 μm or less, and more preferably 0.05 μm or less. The primary particle size of the extender pigment (P) is usually 0.01 μm or more.

The content of the extender pigment (P) is preferably from 0.5 to 10% by mass, more preferably from 1 to 7% by mass, and even more preferably from 1.5 to 5% by mass based on the total solid content of the colored curable resin composition %. When the content ratio of the extender pigment (P) is within the aforementioned range, it is advantageous in improving solvent resistance and heat resistance.

[7] Solvent (E)

The colored curable resin composition of the present invention may further contain a solvent (E). The solvent (E) is not particularly limited, and a solvent generally used in the technical field can be used as the solvent (E). For example, ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), ether ester solvents (containing -COO- and -O- solvents), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (solvents containing OH but not -O-, -CO- and -COO- in the molecule) , Aromatic hydrocarbon solvents, amide solvents, Dimethyl sulfoxide and so on.

As the ester solvent, for example, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, propylene Butyl Butyrate, Isopropyl Butyrate, Ethyl Butyrate, Butyl Butyrate, Methyl Pyruvate, Ethyl Pyruvate, Propyl Pyruvate, Methyl Acetate, Ethyl Acetate, Cyclohexanol Acetate and γ-butyrolactone, etc.

As the ether solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene two Alcohol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, Tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol Dibutyl ether, anisole, phenethyl ether and methyl anisole, etc.

As the ether ester solvent, for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , 2-Methoxy Propionate, 2-Ethoxy Methyl Propionate, 2-Ethoxy Ethyl Propionate, 2-Methoxy-2-Methyl Propionate, 2-Ethoxy Ethyl-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl Ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate, etc.

As the ketone solvent, for example 4-hydroxy-4-ethyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone , Cyclopentanone, cyclohexanone and isophorone, etc.

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

As the aromatic hydrocarbon solvent, for example, benzene, toluene, xylene, trimethylbenzene and the like.

As the amide solvent, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

Among the above-mentioned solvents, in terms of coating properties and drying properties, it is more desirable to be an organic solvent having a boiling point of 120°C or more and 180°C or less at 1 atm. As a solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxy ethyl propionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethyl are preferred. Glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and Ethyl 3-ethoxypropionate.

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

[8] Leveling agent (F)

The colored curable resin composition of the present invention may further contain a leveling agent (F). As the leveling agent (F), for example (does not have a fluorine atom) a silicone-based surfactant, a fluorine-based surfactant, a silicone-based surfactant having a fluorine atom, and the like. These may have a polymerizable group in the side chain.

As the polysiloxane-based surfactant (which does not have a fluorine atom), for example, a surfactant having a siloxane bond in the molecule, and the like. Specifically, for example, TORAY SILICONE DC3PA, the same SH7PA, the same DC11PA, the same SH21PA, the same SH28PA, the same SH29PA, the same SH30PA, the same SH8400 (trade name: TORAY‧DOW CORNING (stock) system), 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 contract company), etc.

As the aforementioned fluorine-based surfactant, for example, a surfactant having a fluorocarbon chain in the molecule, and the like. Specifically, for example, FLUORAD (registered trademark) FC430, the same FC431 (Sumitomo 3M (stock) system), Megafac (registered trademark) F142D, the same F171, the same F172, the same F173, the same F177, the same F183, the same F554, the same R30, Same as RS-718-K (DIC (share) system), EFTOP (registered trademark) EF301, same as EF303, same as EF351, same as EF352 (Mitsubishi Materials Electronic Chemicals (share) system), SURFLON (registered trademark) S381, same as S382, Same as SC101, same as SC105 (Asahi Glass Co., Ltd.) and E5844 ((share) Daikin Institute of Fine Chemicals) 制) etc.

As the aforementioned polysiloxane-based surfactant having a fluorine atom, for example, a surfactant having a siloxane bond and a fluorocarbon chain in the molecule, and the like. Specifically, for example, Megafac (registered trademark) R08, the same BL20, the same F475, the same F477, and the same F443 (DIC (stock) system), etc.

The content ratio of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, with respect to the total amount of the colored curable resin composition 0.01% by mass or more and 0.05% by mass or less. In addition, at this content ratio, the aforementioned pigment dispersant is not included. When the content ratio of the leveling agent (F) is within the aforementioned range, the flatness of the color filter can be improved.

[9] Other ingredients

The colored curable resin composition of the present invention may further include other conventional additives in the technical field such as other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and the like.

<Manufacturing method of colored curable resin composition>

The coloring and curable resin composition of the present invention can be mixed with colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D) and extender pigment (P), and a solvent used as needed (E), a leveling agent (F), a polymerization initiator (D1), and other components are prepared.

Lake pigments are pre-mixed with part or all of the solvent (E) until the average particle size of the colored pigments is about 0.2μm or less. However, it is ideal to use a ball mill to disperse. At this time, if necessary, part or all of the aforementioned pigment dispersant and resin (B) can be prepared. When the colorant (A) further contains a color pigment, it is preferable to prepare a dispersion liquid of the color pigment in the same manner as the dispersion liquid of the lake pigment.

The extender pigment (P) is preferably mixed with part or all of the solvent (E) in advance and dispersed using a ball mill or the like. It is also possible to mix and disperse the coloring pigment and the extender pigment (P) at the same time. In the pigment dispersion liquid obtained in this way, by mixing the remaining components to a predetermined concentration, the intended coloring curable resin composition can be prepared.

When the colorant (A) contains a dye, the dye can be dissolved in part or all of the solvent (E) in advance to prepare a solution. The solution is preferably filtered with a filter with a pore size of about 0.01 to 1 μm.

The mixed colored curable resin composition is preferably filtered with a filter with a pore size of about 0.01 to 10 μm.

<Manufacturing method of color filter>

The colored curable resin composition of the present invention is suitable as a material for color filters. The color filter formed from the colored curable resin composition of the present invention is also one of the present invention.

The color filter of the present invention may include the steps of applying the colored curable resin composition to a substrate, drying it to form a colored composition layer, and curing the colored composition layer by exposure The method is formed. The color filter of the present invention has a colored pattern and a colored coating film.

As a specific method for producing a colored pattern, for example, a photolithography method, an inkjet method, a printing method, and the like. Among them, the lithography method is more ideal. The photolithography method is a method of applying the colored curable resin composition to a substrate, drying it to form a colored composition layer, and exposing the colored composition layer through a photomask to develop images. In the photolithography method, the colored coating film of the hardened substance of the colored composition layer can be formed by not using a photomask and/or not developing the image during exposure.

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

As the substrate, for example, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass coated with silica, polycarbonate, polymethyl methacrylate, and polyterephthalate can be used. A resin plate such as ethylene formate, silicon, or the aforementioned substrate on which aluminum, silver, silver/copper/palladium alloy thin films, etc. are formed. Other color filter layers, resin layers, transistors, circuits, etc. are formed on these substrates.

The formation of pixels of various colors by the lithography method can be carried out with conventional or customary equipment and conditions. For example, it is made in the following way.

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

As the coating method, for example, a spin coating method, a slit coating method, a slit and spin coating method, and the like.

The temperature at the time of heating and drying is preferably 30 to 120°C, more preferably 50 to 110°C. Moreover, as a heating time, it is ideal It is 10 seconds to 60 minutes, more desirably 30 seconds to 30 minutes.

In the case of drying under reduced pressure, it is preferable to perform the drying at a pressure of 50 to 150 Pa and a temperature range of 20 to 25°C.

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

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

The light source used for exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. For example, for light of less than 350 nm, a filter that blocks the wavelength range is used to block, or for light in the vicinity of 436 nm, 408 nm, and 365 nm, it is selectively extracted using a band pass filter that extracts the wavelength range. Specifically, for example, mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, and the like.

Since parallel light can be uniformly irradiated to the entire exposure surface, and the correct position of the mask and the substrate on which the colored composition layer is formed can be aligned, it is ideal to use an exposure device such as a mask positioner and a stepper.

The exposed colored composition layer is contacted with a developing solution, and a colored pattern is formed on the substrate through development. By developing, the unexposed part of the colored composition layer is dissolved in the developing solution and removed. As the developing solution, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide are preferable. The concentration in the aqueous solution of these basic compounds is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. Furthermore, the developer solution may also contain a surfactant.

The imaging method may be any of paddle method, immersion method, spray method, etc. Furthermore, the substrate can be tilted at any angle during development. It is ideal to wash with water after development.

Furthermore, it is ideal to post-bak the resulting colored 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 colored curable resin composition of the present invention, a color filter with excellent heat resistance and solvent resistance can be manufactured. This color filter can be used as a color filter used in display devices (liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements.

[Example]

Hereinafter, the coloring curable resin composition of the present invention will be explained in more detail with reference to examples. The "%" and "parts" in the examples are mass% and mass parts unless otherwise specified.

<Production Example 1: Preparation of Lake Pigment (A1)>

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

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

The following reactions were carried out in a nitrogen atmosphere. After putting 8 parts of the compound represented by the said formula (A-II-18) and 396 parts of methanol into the flask equipped with a cooling pipe and a stirring device, it stirred at room temperature for 30 minutes, and prepared the blue solution. Then, after adding 396 parts of water to this blue solution, it was stirred at room temperature for 30 minutes to obtain a reaction solution.

53 parts of water was put into the beaker, 11.8 parts of Keggin structure type phosphotungstic acid (manufactured by Aldrich) and 53 parts of methanol were put into the water, and mixed in an air environment and at room temperature to prepare a phosphotungstic acid solution. The obtained phosphotungstic acid solution was dropped into the previously prepared reaction solution over 1 hour. After stirring for 30 minutes at room temperature, it was 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 filtration operation was repeated twice. The blue solid obtained by this operation was put into 200 parts of water and dispersed for 1 hour, and then the filtration operation was repeated twice. The blue solid obtained by this operation was dried at 60°C under reduced pressure to obtain 17.1 parts of the compound represented by formula (A-I-18) [lake pigment (A1)].

<Preparation of dispersion>

14 parts of compound represented by formula (AI-18), 2.5 parts of dispersant (BYK (registered trademark)-LPN6919 (manufactured by BYK-Chemie Japan)), 6 parts of resin (B1) (converted solid content), propylene glycol monomethyl 77.5 parts of ether acetate and 300 parts of 0.2 mm zirconia particles were shaken for 6 hours using a paint conditioner (manufactured by Red Devil) to prepare a dispersion (A1).

<Production Example 2: Preparation of Dibenzopyran Dye (A2)>

Mix 20 parts of the compound represented by formula (1x) and 200 parts of N-propyl-2,6-dimethylaniline (manufactured by Wako Pure Chemical Industries, Ltd.) under light-shielding conditions, and stir the resulting solution at 110°C 6 hours. After cooling the obtained reaction solution to room temperature, it was added to a mixed solution of 800 parts of water and 50 parts of 35% by mass hydrochloric acid, and after stirring at room temperature for 1 hour, crystals were precipitated. The precipitated crystal was filtered with suction to obtain a residue, and then dried to obtain a compound represented by the formula (1-32) [dibenzopyran dye (A2)].

<Production Example 3: Preparation of Resin (B1)>

In a flask equipped with a reflux cooler, a dropping funnel and a stirrer, flow in an appropriate amount of nitrogen to replace the nitrogen environment, and put in propylene glycol monomethyl ether acetate 280 parts, heated to 80°C while stirring.

Then, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-acrylate and/or 3,4-epoxytricyclo[5.2 .1.0 ^{A mixed solution of 289 parts of a mixture of 2,6} ]decane-9-ester and 125 parts of propylene glycol monomethyl ether acetate.

On the other hand, a mixed solution of 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 235 parts of propylene glycol monomethyl ether acetate was dropped over 6 hours. After the dripping is finished, keep at the same temperature for 4 hours, and then cool to room temperature to obtain a resin (B1) with a type B viscosity (23°C) of 125 mPas, a solid content of 35.1%, and an acid value of 115 mg-KOH/g in terms of solid content. Solution. The weight average molecular weight (Mw) of the resin (B1) was 1.06×10 ⁴ , and the degree of dispersion was 2.08.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin was performed using the GPC method under the following conditions.

Installation; K2479 (manufactured by Shimadzu Corporation)

String; SHIMADZU Shim-pack GPC-80M

Column temperature; 40℃

Solvent; Tetrahydrofuran [THF]

Flow rate; 1.0mL/min

Sensor; RI

Standard materials for calibration; TSK standard polystyrene F-40, F-4, F-288, A-2500, A-500 (TOSOH (stock) system).

The ratio (Mw/Mn) of the weight average molecular weight (Mw) of the converted polystyrene to the number average molecular weight (Mn) obtained above is the degree of dispersion.

<Examples 1 to 4, Comparative Example 1> (1) Preparation of colored curable resin composition

The components described in Table 1 were mixed to obtain a colored curable resin composition. The unit of the blending amount of each component in Table 1 is "parts by mass". As described later, with regard to lake pigments (A1) and extender pigments (P1) to (P4), the dispersant, resin (B1) and solvent (E1) or (E4) are mixed in advance to form a dispersion and used for coloring The preparation of the curable resin composition is shown in Table 1, showing the content of each component contained in the finally obtained colored curable resin composition. The numerical value in Table 1 is the amount of solid content (parts by mass) of each component.

Resin (B1): Shows the total content of resin (B1).

Solvent (E1): Represents the total content of propylene glycol monomethyl ether acetate.

In addition, in Table 1, each component is as shown below. Moreover, resin (B1) shows the mass part of solid content conversion.

[1] Dispersion (A1): Dispersion (1)

[2] Dye (A2): Compound represented by formula (1-32) obtained in Production Example 2

[3] Resin (B1): Resin (B1) obtained in Production Example 3

[4] Polymeric compound (C1): Dineopentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

[5] Polymerization initiator (D1): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE 01 ; Made by BASF; oxime compound)

[6] Extender pigment dispersion (P1): zinc oxide dispersion. When preparing the colored curable resin composition, use a dispersion obtained by pre-mixing zinc oxide (10 parts), acrylic pigment dispersant (1.3 parts), and the solvent (E1) (88.7 parts) shown in Table 1 as the formulation Element.

[7] Extender pigment dispersion liquid (P2): Titanium oxide dispersion liquid. When preparing the colored curable resin composition, use a dispersion obtained by mixing titanium oxide (10 parts), acrylic pigment dispersant (3 parts), and the solvent (E1) (87 parts) shown in Table 1 as the preparation. Element.

[8] Extender pigment dispersion (P3): Silica dispersion (PGM-AC-0413; manufactured by Nissan Chemical Industry Co., Ltd., containing 30% extender)

[9] Extender pigment dispersion (P4): Zirconia dispersion (SZR; manufactured by Sakai Chemical Co., containing 30% extender)

[10] Solvent (E1): propylene glycol monomethyl ether acetate

[11] Solvent (E2): ethyl lactate

[12] Solvent (E3): propylene glycol diacetate

[13] Solvent (E4): propylene glycol monomethyl ether

[14] Leveling agent (F1): polyether modified silicone oil (TORAY SILICONE SH8400; TORAY‧DOW CORNING (share system)

(2) Production of colored coating film

On a 5cm square glass substrate (EAGLE2000; manufactured by Corning), the colored curable resin composition was applied by spin coating to make the post-baked film thickness 2μm, and then prebaked at 100°C for 3 minutes to form Colored composition layer. After being left to cool, an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) was used to irradiate the colored composition layer with light at an exposure amount of ^{150 mJ/cm 2 (365 nm as a reference) in an atmospheric environment.} After light irradiation, post-baking was performed in an oven at 230°C for 20 minutes to obtain a colored coating film.

(3) Chromaticity evaluation

For the resulting colored coating film, use a color measuring machine (OSP-SP-200; manufactured by OLYMPUS (stock)) to measure the spectroscopy, and use the characteristic function of the C light source to measure the xy chromaticity coordinates of the CIE XYZ color system (x, y) and stimulus value Y. The larger the value of Y, the higher the brightness. The results are shown in Table 2.

(4) Heat resistance evaluation

Heat the resulting colored coating film in an oven at 230°C for 2 hours. The xy chromaticity coordinates (x, y) and Y before and after heating are measured, and from the measured values, the color difference ΔEab* is calculated by the method described in JIS Z 8730:2009 (7. Color difference calculation method). The calculated value obtained is converted into a relative value (%) when ΔEab* of Comparative Example 1 is 100%. The results are shown in Table 2.

(5) Evaluation of solvent resistance

The resulting colored coating film was immersed in an excessive amount of N-methyl-2-pyrrolidone maintained at a constant temperature of 23°C for 40 minutes, and then thoroughly washed with water. The xy chromaticity coordinates (x, y) and Y before and after immersion were measured, and from the measured values, the color difference ΔEab* was calculated by the method described in JIS Z 8730:2009 (7. Color difference calculation method). The calculated value obtained is converted into a relative value (%) when ΔEab* of Comparative Example 1 is 100%. The results are shown in Table 2.

<Comparative Example 2>

(A) Coloring agent; mixed

C.I. Pigment Blue 15: 6 (pigment) 29.5 parts

Acrylic pigment dispersant 15 parts

198 parts of propylene glycol monomethyl ether acetate

Using a ball mill, by dispersing the pigments and then mixing

(A) Dispersion (A1); Dispersion (1) 82 parts

(B) Resin; Resin (B1) (converted solid content) 50 parts

(C) Polymeric compound; (C-1) Dineopentaerythritol hexaacrylate (KAYARAD DPHA; Nippon Kayaku Co., Ltd.) 50 parts

(D) Polymerization initiator; (D-1); N-benzyloxy-1-(4-phenylhydrosulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) ) OXE 01; made by BASF; oxime compound) 14 parts

(F) Leveling agent; (F-1); Polyether modified silicone oil (TORAY SILICONE SH8400; TORAY‧DOW CORNING (stock) system) 0.1 part

(E) Solvent; (E-1); Propylene glycol monomethyl ether acetate 597 parts

(E) Solvent; (E-4); 149 parts of propylene glycol monomethyl ether to obtain a colored curable resin composition.

Then, following the procedure described in "(2) Production of Colored Coating Film" above, a colored coating film was produced from the obtained colored curable resin composition. With respect to the resulting colored coating film, the same chromaticity evaluation, heat resistance evaluation, and solvent resistance evaluation were performed in the same manner as in Examples 1 to 4 and Comparative Example 1. The results are shown in Table 2.

(Industrial use possibility)

According to the colored curable resin composition of the present invention, a color filter with improved solvent resistance and heat resistance can be produced.

Claims (6)

A coloring and curable resin composition containing: colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D) and extender pigment (P), and does not contain silsesquioxane ; Relative to the total solid content of the colored curable resin composition, the content of the extender pigment (P) is 0.5 to 10% by mass; wherein the colorant contains lake pigments. The coloring and curable resin composition described in item 1 of the scope of the patent application, wherein the lake pigment is composed of an anion and a compound containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen. Compound (Aa) composed of cations of pigment skeleton. The colored curable resin composition described in item 2 of the scope of patent application, wherein the aforementioned compound (Aa) is a compound represented by formula (AI), [X ⁺ ] _m [Y] ^m- (AI) formula (AI) Where X ⁺ represents a cation represented by formula (AIX);

[Y] ^m- represents an m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen; m represents any natural number; in formula (AIX), R ⁴¹ to R ^{44 are} mutually Independently represent a monovalent saturated hydrocarbon group with 1 to 20 carbons, an alkyl group with 2 to 20 carbons which may have a substituent, and a group in which an oxygen atom is inserted between the methylene groups constituting the alkyl group (but a plurality of oxygen atoms will not (Inserted in a contiguous manner), a monovalent aromatic hydrocarbon group having 6 to 14 carbons which may have a substituent, an aralkyl group having 7 to 11 carbons which may have a substituent or a hydrogen atom; R ⁴¹ and R ⁴² may be bonded , And together with these bonded nitrogen atoms to form a ring, R ⁴³ and R ⁴⁴ can be bonded, and together with these bonded nitrogen atoms to form a ring; R ⁴⁷ to R ⁵⁴ independently represent a hydrogen atom, Halogen atom, nitro group, hydroxyl group or C1-C8 alkyl group. When the carbon number is 2 or more, oxygen atoms may be inserted between the methylene groups constituting the alkyl group (but the plural oxygen atoms will not be adjacent to each other). Way to insert); R ⁴⁸ and R ⁵² can bond to each other to form -NH-, -O-, -S- or -SO ₂ -; T ¹ represents a monovalent aromatic heterocyclic group that may have a substituent; m is In the case of a natural number of 2 or more, a plurality of X ⁺ may have the same structure or different structures. The coloring curable resin composition according to item 1 or 2 of the scope of patent application, wherein the extender pigment (P) is at least one selected from the group consisting of zinc oxide, titanium oxide, silicon oxide, and zirconium oxide. A color filter, which is formed of the colored hardening resin composition as described in item 1 or 2 of the scope of patent application. A display device includes the color filter described in item 5 of the scope of patent application.