TW201807080A - 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 same

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

A coloring hardening resin composition including a coloring agent dispersion liquid in which a coloring agent containing a dye and a pigment, an extender pigment and a dispersant are dispersed in a solvent containing propylene glycol monomethyl ether acetate, a polymerizable compound and a polymerization initiator is known (Japanese Patent Application Publication No. 2015-98590).

The present invention provides a coloring curable resin composition, a color filter, and a display device described below.

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

[2] The colored hardening resin composition according to [1], wherein the lake pigment is an anion and a pigment having a compound containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen. Skeleton Sun (Aa).

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

[In the formula (AI), X ⁺ represents a cation represented by the 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 an arbitrary natural number; and in formula (AIX), R ⁴¹ to R ^{44 are} mutually Independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms which may have a substituent, and an oxygen atom is interposed between the methylene groups constituting the alkyl group (however, plural oxygen atoms do not Inserted adjacently), a monovalent aromatic hydrocarbon group having 6 to 14 carbons which may have a substituent, an aralkyl group or hydrogen atom having 7 to 11 carbons which may have a substituent; R ⁴¹ and R ⁴² may be bonded And form a ring together with the nitrogen atoms bonded to them, R ⁴³ and R ⁴⁴ may be bonded and form a ring together with the nitrogen atoms bonded to them; R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, When a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms has 2 or more carbon atoms, an oxygen atom may be inserted between the methylene groups constituting the alkyl group (but a plurality of oxygen atoms will not be adjacent to each other). Insertion); 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; m is 2 or more Natural number of hours X ⁺ may be a plurality of the same structure, it may also be a different configuration].

[4] The colored hardening 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 zirconia. 1 species.

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

[6] A display device including the color filter according to [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 a constitution pigment (P), wherein the colorant (A) contains a color Deposit pigment.

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

In addition, in the present specification, the combination of each component is exemplified. Unless otherwise stated, they may be used alone or in combination.

[1] Colorant (A) [1-1] Lake pigment

The colorant (A) contains a lake pigment.

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

As dyes that can form lake pigments, such as acid dyes, basic dyes, and direct dyes, they can be used in color indexes (published by The Society of Dyers and Colorists) to be classified as having hue in addition to pigments. Compounds, conventional dyes described in Dyeing Notes (Dyeing Company).

As specific examples of the acid dye, 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 oranges 7, 10, 11, 12, 15, 19, 20, 22, 28, 30, 52, 56, 74, 127; CI acid Purple 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, 16, 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.

Specific examples of direct dyes include C.I. direct blue 41, 77, 86, 87, 106, 107, 108, 109, 189, 190, 199, 264; C.I. Direct Purple 54.

Specific examples of the lake-forming agent include barium chloride, calcium chloride, ammonium sulfate, aluminum chloride, aluminum acetate, lead acetate, tannic acid, Catanol, Tamol, heteropoly acids (phosphotungstic acid, phosphomolybdic acid) , Phosphotungstic molybdic acid, silicotungstic acid, silomotungstic acid, silicotungstic molybdic acid, etc.), heteropolyacids (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, 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 a cation derived from the dye described above or an anion derived from the dye described above. The lake pigment preferably has a cation derived from the dye.

Examples of the cation derived from the dye include cations derived from a triarylmethane dye, a Rhodamine dye, and a xanthene dye. The cations from the above dyes are A triarylmethane dye is preferable, and a triarylmethane dye which can have a heterocyclic ring, such as a thiazolyl group, is more preferable.

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

The anionic lake pigment, in addition to a heteropolyacid ion (M _m1 O _n) ^c-, a heteropolyacid ion _{(X 1 M m1 O n)} c- ( formulas, M is a multi-atom, X represents a hetero atom, 1 represents a composition ratio of heteroatoms, m1 represents a composition ratio of polyatoms, n represents a composition ratio of oxygen atoms, and c represents an integer of 1 to 8), for example, 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 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. Or a reactive group. However, at least one of R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ is a reactive group.)

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

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

The lake pigment of the present invention is more preferably a basic dye (triaryl methane-based dye, rose red-based dye, etc.) and a polyacid lake pigment.

Acid-based complex oxoacid acid condensation, can be a heteropolyacid ion (M _m1 O _n) ^c-, may also be a heteropolyacid ion _{(X 1 M m1 O n)} c-. In the formula, M represents a polyatom, X represents a heteroatom, 1 represents a composition ratio of heteroatoms, m1 represents a composition ratio of polyatoms, n represents a composition ratio of oxygen atoms, and c represents an integer of 1 to 8.

Examples of the polyatom M include W, Mo, V, Ti, and Nb.

Examples of the hetero atom X include Si, P, As, S, Fe, Co et al.

From the viewpoints of solvent resistance, heat resistance, and the like, specific examples of preferred polyacids include heteropolyacids such as tungstic acid ion [W ₁₀ O ₃₂ ] ^4- , molybdic acid ion [Mo ₆ O ₁₉ ] ^2-, and the like. ; Phosphotungstic acid ion [PW ₁₂ O ₄₀ ] ^3- , Silotungstic acid ion [SiW ₁₂ O ₄₀ ] ^4- , Phosphomolybdic acid ion [PMo ₁₂ O ₄₀ ] ^3- , Phosphotungstic molybdate ion [PW _12-x Heteropoly acids such as Mo _x O ₄₀ ] ^3- and H ₃ [PW _2-x Mo _x O ₇ ] ^4- . More specifically, for example, phosphotungstic molybdate 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 these, from the viewpoints of solvent resistance, heat resistance, and the like, the compound (Aa) is preferably a compound represented by the formula (AI): [X ⁺ ] _m [Y] ^m- (AI).

In formula (AI), 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 W, Mo, Si, and P and oxygen. m represents an arbitrary natural number.

In the formula (AIX), R ⁴¹ to R ⁴⁴ independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms which may have a substituent, and an intermethylene group constituting the alkyl group. An oxygen atom group (but plural oxygen atoms are not inserted adjacently), a monovalent aromatic hydrocarbon group having 6 to 14 carbons which may have a substituent, and an arane having 7 to 11 carbons which may have a substituent Radical or hydrogen atom. R ⁴¹ and R ⁴² may be bonded to form a ring with the nitrogen atoms to which they are bonded, and R ⁴³ and R ⁴⁴ may be bonded to form a ring with the nitrogen atoms to which they are bonded.

R ⁴⁷ to R ⁵⁴ each 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 carbon atoms, and a carbon number of 2 or more, An oxygen atom may be inserted between the methylene groups constituting the alkyl group (however, a plurality of oxygen atoms are not 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 the monovalent saturated hydrocarbon group 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 Alkyl, dodecyl, hexadecyl, eicosyl, etc. linear alkyl groups having 1 to 20 carbon atoms; isopropyl, isobutyl, second butyl, third butyl, isopentyl 3 to 20 branched chain alkyl groups such as alkyl, neopentyl, and 2-ethylhexyl; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms and the like. More preferably, it is a linear or branched alkyl group having 1 to 12 carbons, more preferably it is a linear or branched alkyl group having 1 to 8 carbons, and even more preferably a straight chain having 1 to 6 carbon atoms. Or branched chain alkyl.

Examples of the substituent which the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms may have include a halogen atom (fluorine atom, chlorine atom, bromine atom, or iodine atom), a cyano group, a nitro group, a hydroxyl group, a substituted or unsubstituted amine group, and the like. .

Regarding R ⁴¹ to R ⁴⁴ , a group having 2 to 20 carbons and an oxygen atom interposed between 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, and the like. Examples of the alkyl group having 2 to 20 carbon atoms include ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and eicosane Straight-chain alkyl groups having 2 to 20 carbons; isopropyl, isobutyl, 2butyl, 3butyl, isopentyl, neopentyl, 2-ethylhexyl, etc. 3 to 20 branched chain alkyl groups. More preferably, it is a linear or branched alkyl group having 2 to 12 carbons, more preferably it is a linear or branched alkyl group having 2 to 8 carbons, and even more preferably a straight chain having 2 to 6 carbon atoms. Or branched chain alkyl.

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

Examples of the aralkyl group having 7 to 11 carbon atoms represented by R ⁴¹ to R ⁴⁴ include benzyl, phenethyl, phenylpropyl, 2-methylphenylmethyl, 3-methylphenylmethyl, 4 -Methylphenylmethyl, 2,3-dimethylphenylmethyl, 2,4-dimethylphenylmethyl, 2,5-dimethylphenylmethyl, 2,6-dimethyl Phenylphenylmethyl, 3,4-dimethylphenylmethyl and naphthylmethyl.

As the substituent which the aralkyl group having 7 to 11 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, a substituted or unsubstituted Amine groups, etc.

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

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

Examples of the alkyl group 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; isopropyl A branched alkyl group such as an alkyl group, an isobutyl group, a second butyl group, a third butyl group, an isopentyl group, a neopentyl group, and a 2-ethylhexyl group. More preferably, it is an alkyl group having 1 to 6 carbon atoms, and more preferably, it is methyl, ethyl, propyl, or butyl.

Regarding R ⁴⁷ to R ⁵⁴ , an 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,- A CH ₂ -O-CH ₃ group, a -CH ₂ -O-CH ₂ -CH ₃ group, a -CH ₂ -CH ₂ -O-CH ₂ -CH ₃ group, and the like.

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 and polycyclic, such as pyrrole, furan, thiophene, imidazole, pyrazole, oxazole, isoxazole , Thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, trazine, quinoline, isoquinoline, quinazoline , Indole, benzimidazole, benzofuran, purine, acridine, phenoxazine, phenothiazine, and the like.

Examples of the substituent which the aromatic heterocyclic group may have include a halogen atom (fluorine atom, chlorine atom, bromine atom, or iodine atom), a cyano group, a nitro group, a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, and a carbon number 1 To 8 alkyl groups, substituted or unsubstituted phenyl groups, substituted or unsubstituted amine groups, 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 an arbitrary natural number.

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

[1-2] Dyes

The colorant (A) may contain a dye in addition to the lake pigment.

The dye is not particularly limited, and conventional dyes such as solvent dyes, acid dyes, direct dyes, and mordant dyes can be used. As the dye, for example, in the color index (published by The Society of Dyers and Colorists), compounds other than pigments are classified as compounds having a hue, and conventional dyes described in dyeing notes (color dyeing companies). Furthermore, depending on the chemical structure, for example, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinimine dyes, methine Base dyes, methine azo dyes, square dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, and the like. Of these, 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 Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc .; CI Acid Yellow 1 , 3, 7, 9, 11, 11, 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, 10 9, 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 , 104, 105, 106, 109, etc. CI acid dyes; 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, 12 0, 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 Disperse Yellow 51, 54 , 76; CI disperse violet 26, 27; CI disperse dyes such as CI disperse blue 1, 14, 56, 60; 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 Green and other CI basic dyes; CI Reactive Yellow 2, 76, 116; CI Reactive Orange 16; CI Reactive Red 36 and other CI reactive dyes; 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 oranges 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, etc. CI mordant dyes, CI reducing green 1 and other CI reducing dyes.

These dyes can be appropriately selected in accordance with the spectral spectrum of the desired color filter.

Among these, when a dye is used, it is preferable to include a dibenzopiperan dye from the viewpoint of solvent resistance, heat resistance, and the like, and from the viewpoint of obtaining good brightness.

A dibenzopiperan dye is a dye containing a compound having a dibenzopiperan skeleton in the molecule. Examples of dibenzopiperan dyes include 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 (Bengali Rose Red B); Sulfur Rose Red B; Dibenzopiperan dyeing described in Japanese Patent Application Laid-Open No. 2010-32999 And the dibenzopiperan dyes described in Japanese Patent No. 4492760. Among them, those dissolved in an organic solvent are preferable.

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

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

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

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 each 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 ⁺ . The four R ¹¹ may be the same or different.

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

R ⁹ and R ¹⁰ independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ -contained in the saturated hydrocarbon group may be -O-, -CO-, -NH- or -NR ⁸ -substitution, and R ⁹ and R ¹⁰ may be bonded to each other to form a 3 to 10 membered heterocyclic ring containing a nitrogen atom.

R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. In formula (1a), there are cases where -SO ₃ ^- is one, and the number is one.

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

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 . As the case of -SO ₃ ^- Z ^+, is desirable as ^{_{-SO 3 - + N (R 11}} ) 4. When R ¹ to R ^{4 are} such a group, a color filter having less foreign matter generation and better solvent resistance and heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (1a).

R ¹ to R ⁴ and R ⁸ to R ^{11 are} monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl , Alkyl, decyl, dodecyl, cetyl, eicosyl, etc .; branches of isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl, etc. A chain alkyl group; a cycloaliphatic saturated hydrocarbon group having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl, and the like.

The hydrogen atom contained in the saturated hydrocarbon group of R ¹ to R ⁴ may be substituted by a halogen atom, for example.

Examples of the aralkyl group represented by R ¹ to R ^{4 are the} same 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, for example, by a hydroxyl group or a halogen atom.

Examples of the ring formed by R ¹ and R ² and the ring formed by R ³ and R ⁴ are as follows.

Examples of -OR ⁸ include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, and eicosyloxy. Base etc.

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

Examples of -SR ⁸ include methylhydrosulfanyl, ethylhydrosulfanyl, butylhydrosulfanyl, hexylhydrosulfanyl, decylhydrosulfanyl, and eicosylhydrosulfanyl.

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

Examples of -SO ₃ R ⁸ include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, third butoxysulfonyl, hexylsulfonyl, and eicosyloxy. Sulfonyl.

Examples of -SO ₂ NR ⁹ R ¹⁰ include sulfamoyl groups; N-methylaminosulfonyl groups, N-ethylaminesulfonyl groups, N-propylaminesulfonyl groups, and N-isopropylaminesulfonyl groups. Group, N-butylaminosulfonyl, N-isobutylaminesulfonyl, N-second butylaminesulfonyl, N-thirdbutylaminesulfonyl, N-pentylaminesulfonyl N- (1-ethylpropyl) aminosulfonyl, N- (1,1-dimethylpropyl) aminosulfonyl, N- (1,2-dimethylpropyl) aminosulfonyl Fluorenyl, N- (2,2-dimethylpropyl) aminosulfonyl, N- (1-methylbutyl) aminesulfonyl, N- (2-methylbutyl) aminesulfonyl , N- (3-methylbutyl) sulfamidino, N-cyclopentylaminesulfonyl, N-hexylaminesulfonyl, N- (1,3-dimethylbutyl) sulfamo Group, N- (3,3-dimethylbutyl) aminosulfonyl group, N-heptylaminesulfonyl group, N- (1-methylhexyl) aminesulfonyl group, N- (1,4- Dimethylpentyl) sulfamoyl, N-octylaminesulfonyl, N- (2-ethylhexyl) aminesulfonyl, N- (1,5-dimethyl) hexylaminesulfonyl N-1 substituted amine sulfonyl groups such as N, (1,1,2,2-tetramethylbutyl) sulfamoyl groups; N, N-dimethylamine sulfonyl groups, N, N-ethyl Methylmethylsulfonyl, N, N-diethylaminesulfonyl, N, N-propylmethyl Sulfonyl, N, N-isopropylmethylaminesulfonyl, N, N-third butylmethylaminesulfonyl, N, N-butylethylaminesulfonyl, N, N-bis ( N, N-2 substituted aminesulfonyl groups such as 1-methylpropyl) sulfamoyl, N, N-heptylmethylaminesulfonyl 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 is} more preferable.

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

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

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

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

Among the aforementioned ⁺ N (R ¹¹ ) ₄ , at least two of the four R ¹¹ are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbons 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, a color filter with few foreign matters can be formed from the colored hardening resin composition of the present invention containing the compound (1a). sheet.

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

In the formula (2a), R ²¹ to R ²⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. R ²¹ and R ²² may form a ring containing a nitrogen atom together, and R ²³ and R ²⁴ may form a ring containing a nitrogen atom together.

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

m1 represents an integer 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 ⁺ . The four R ²⁷ may be the same or different.

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

In the formula (2a), R ²¹ to R ²⁴ having a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms are, for example, the same groups as those exemplified for 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 the formula (2a), R ²¹ and R ²³ are hydrogen atoms, and R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms. The hydrogen atoms contained in the aromatic hydrocarbon groups are -SO ₃ ^- ,- Substituents such as SO ₃ H, -SO ₃ ^- Z1 ⁺ , -SO ₃ R ²⁶ or -SO ₂ NHR ^{26 are} preferred.

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

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

The nitrogen atom-containing ring formed by R ²¹ and R ²² and the nitrogen atom-containing ring formed by R ³ and R ⁴ are, for example, the same ring as the ring formed by R ¹ and R ² . Among them, aliphatic heterocycles are preferred. Examples of the aliphatic heterocyclic ring include the following rings.

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

The saturated hydrocarbon group represented by R ²¹ to R ²⁴ is preferably 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, a color filter having better solvent resistance and heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (2a).

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

Among the aforementioned ⁺ N (R ²⁷ ) ₄ , at least two of the four R ²⁷ are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total carbon number of the four R ²⁷ is preferably 20 to 80, and more preferably 20 to 60. When ⁺ N (R ²⁷ ) ₄ is present in the compound (2a), when R ^{27 is} such a group, solvent resistance and heat resistance can be formed from the colored hardening resin composition of the present invention containing the compound (2a). Better color filters.

m1 is preferably 1 to 4, and more preferably 1 or 2.

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

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

R ³³ and R ³⁴ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkyl hydrogenthio group having 1 to 4 carbon atoms or an alkylsulfonyl group having 1 to 4 carbon atoms.

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

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

R ¹¹ has the same meaning as described above.

R ³¹ and R ^{32 are} monovalent saturated hydrocarbon groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and the like; Branched alkyl groups 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 as R ³¹ and R ³² include phenylene.

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

R ³¹ and R ³² are each preferably 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 of R ³³ and R ³⁴ include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, second butyl, and third butyl.

Examples of the alkyl hydrogenthio group having 1 to 4 carbon atoms as R ³³ and R ³⁴ include methylhydrothio group, ethylhydrothio group, propylhydrothio group, butylhydrothio group, and isopropylhydrothio group. Wait.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms of R ³³ and R ³⁴ include 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 of 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). In the formula, R ⁴⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, more preferably a branched alkyl group having 6 to 12 carbon atoms, and even 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) are equivalent to compound (2a), and formula (1-24) to formula The compound represented by any one of (1-36) corresponds to compound (3a).

Among these, 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 is preferred. Examples of such compounds include compounds represented by (1-1) to formula (1-8), formula (1-11), or formula (1-12).

In addition, from the point of good solubility in organic solvents, compounds represented by any of (1-24) to formula (1-33) are preferred.

As the dibenzopiperan dye, commercially available dibenzopiperan dyes (for example, "Chugai Aminol Fast Pink RH / C" manufactured by Sinochem Chemical Co., Ltd., and "Rodamin 6G" manufactured by Taoka Chemical Industry Co., Ltd.) can be used. . Furthermore, a commercially available dibenzopiperan dye is used as a starting material, and it can also be synthesized by referring to Japanese Patent Application Laid-Open No. 2010-32999.

[1-3] coloring pigment

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

Examples of color pigments include 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, Yellow pigments such as 153, 154, 166, 173, 194, 214, etc .; CI pigment oranges 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 And other red pigments; CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; CI Pigment Purple 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, blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60, etc. are preferred; purple pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38, etc. The pigment is more preferably CI Pigment Blue 15: 3, 15: 6 and CI Pigment Violet 23, and more preferably CI Pigment Blue 15: 6. By including the coloring pigment, the transmission spectrum can be easily optimized, and the light resistance and solvent resistance of the color filter are improved.

The colored pigment may be subjected to a rosin treatment, a surface treatment using a pigment derivative introduced with an acidic group or a basic group, a graft treatment of the pigment surface by a polymer compound, and the like, if necessary, by a sulfuric acid micronization method, etc. Micronization treatment or removal of impurities by washing with organic solvents, water, etc., removal of ionic impurities by ion exchange methods, etc. Processing, etc.

The particle size of the colored pigment is preferably uniform. When the pigment dispersant is contained in the dispersing treatment, a pigment dispersant can be obtained in a state where the colored pigment is uniformly dispersed in the solution.

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

In the case of using a pigment dispersant, the amount of the pigment dispersant used is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less. When the amount of the pigment dispersant used is in the aforementioned range, there is a tendency that a pigment dispersion liquid in a uniformly dispersed state is obtained.

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

The content ratio of the colorant (A) is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and even more preferably 10 to 50% by total amount of the solid content of the coloring curable resin composition. %. When the content ratio of the colorant (A) is within the above range, the color concentration when the color filter is used is sufficient, and the composition may contain a required amount of the resin (B) and the polymerizable compound (C), and mechanical strength may be formed Full graphics. Here, what is called in this specification The "total amount of solid content" means an amount in which the total content of the colored curable resin composition is excluding the content of the solvent. The total amount of the solid components and the content ratio of each component can be measured, for example, by a conventional analysis means such as liquid chromatography or gas chromatography.

From the viewpoints 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% of the colorant (A) 100% by mass. The mass% is more preferably 75 to 100 mass%, and particularly preferably 90 to 100 mass%.

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

When the colorant (A) contains a coloring pigment, the content ratio of the coloring pigment of the colorant (A) from the viewpoints of solvent resistance and heat resistance is usually 0.1 to 98% of the colorant (A) 100% Mass% is more preferably 0.1 to 60 mass%, more preferably 0.1 to 50 mass%, still more preferably 0.5 to 25 mass%, and particularly preferably 0.5 to 10 mass%.

[2] Resin (B)

The resin (B) is not particularly limited, and is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].

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

Examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, butenoic acid, o-, m-, and p-vinyl benzoic acid; maleic acid, fumaric acid, and lemon lemon Acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic 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-norylene 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 Dicyclo [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 -Carboxyl-containing bicyclic unsaturated compounds such as ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene; 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 anhydride; di [2- (meth) acryloxyethyl] succinate, mono [2- (meth) acryloxyethyl] phthalate, etc. Unsaturated mono [(meth) acryloxyalkyl] esters of polycarboxylic acids; unsaturated acrylates containing hydroxyl and carboxyl groups in the same molecule, such as α- (hydroxymethyl) acrylic acid; etc.

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

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

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

As (b), for example, a monomer (b1) having an epoxyethyl group and an ethylenically unsaturated bond (hereinafter referred to as “(b1)”), a monomer having an oxetanyl group and an ethylenically unsaturated bond Monomer (b2) (hereinafter referred to as "(b2)" (Case)), a monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), and the like.

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

Examples of (b1-1) include glycidyl (meth) acrylate, beta-methylglycidyl (meth) acrylate, beta-ethylglycidyl (meth) acrylate, and glycidyl Vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o- Vinyl benzyl epoxy propyl ether, α-methyl-m-vinyl benzyl epoxy propyl ether, α-methyl-p-vinyl benzyl epoxy propyl ether, 2, 3 -Bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2, 6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) Styrene, 2,3,6-tris (glycidoxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) 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), (meth) acrylic acid 3, 4-epoxycyclohexyl methyl ester (e.g. CYCLOMER A400; manufactured by DAICEL); 3,4-epoxy cyclohexyl methyl (meth) acrylate (e.g. CYCLOMER M100; manufactured by DAICEL); formula A compound represented by (I), a compound represented by formula (II), and the like.

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

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 a bond with O. ]

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

An alkyl group substituted with a hydroxyl group as a hydrogen atom, such as 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, and the like.

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

Examples of the alkanediyl group include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, and pentane-1,5-diyl. Radical, hexane-1,6-diyl and the like.

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 a bond with O).

As the compound represented by formula (I), for example, formulas (I-1) to (I-15) A compound represented by any of them. Among them, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), or formula (I-11) to formula (I) are more preferable. 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).

Examples of the compound represented by the formula (II) include compounds represented by any of the formulae (II-1) to (II-15). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II) are more preferable 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 formula (I) and the compound represented by formula (II) may be used alone, or two or more kinds may be used in combination. When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, the content ratio of these [compounds represented by the formula (I): compounds represented by the formula (II)] is preferably based on Mohr It is 5:95 to 95: 5, and more preferably 20:80 to 80:20.

As (b2), a monomer having an oxetanyl group and a (meth) acryloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloxymethyloxetane, and 3-methyl-3-propenyloxymethyloxetane Butane, 3-ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3- Methacryloxyethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methacryloxyethyloxane Cyclobutane, 3-ethyl-3-propenyloxyethyloxetane, and the like.

As (b3), a monomer having a tetrahydrofuranyl group and a (meth) acrylic fluorenyloxy group is more preferable. Specific examples of (b3) include tetrahydrofuran methyl acrylate (for example, BISCOAT V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and tetrahydrofuran methyl methacrylate.

As (b), the reliability of heat resistance, chemical resistance, etc. of the obtained color filter can be improved more, (b1) is preferable. Furthermore, (b1-2) is more preferable from the viewpoint that the storage stability of the colored curable resin composition is good.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, and third butyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, ( Cyclohexyl methacrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-ester (commonly known in the technical field as " (Dicyclopentyl (meth) acrylate ". Also known as" tricyclodecyl (meth) acrylate "), tricyclo (meth) acrylate [5.2.1.0 ^2,6 ] decene-8 -Esters (commonly known in the technical field as "dicyclopentenyl (meth) acrylate." Also known as "tricyclodecene (meth) acrylate"), dicyclo (meth) acrylate Pentoxyethyl, isoamyl (meth) acrylate, adamantane (meth) acrylate, allyl (meth) acrylate, propynyl (meth) acrylate, phenyl (meth) acrylate, (Meth), such as naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. Acrylates; (meth) acrylates containing hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate; diethyl maleate, fumarate Dicarboxylic acid diesters such as diethyl ester, 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-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyl (Ethyl) 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 Group) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] heptane- 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-thirdbutoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] heptane -2-ene, 5-phenoxycarbonyl bicyclo [2.2.1] hept-2-ene, 5,6-bis (3th butoxycarbonyl) Bicyclic unsaturated compounds such as cyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene; N-phenylmaleinia Amine, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimide-3-maleimide benzoate, N-succinimide -4-maleimide iminobutyrate, N-succinimide imino-6-maleimide iminohexanoate, N-succinimide imino-3-maleimide propionate, N- (9-acridyl) maleimide imide derivatives such as dicarbonylamine; 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 Diene, 2,3-dimethyl-1,3-butadiene; etc.

Among these, from the viewpoints of copolymerization reactivity and heat resistance, styrene, vinyltoluene, N-benzylmaleimide, N-cyclohexylmaleimide, and N-benzene are preferable. Methyl maleimide, bicyclo [2.2.1] hept-2-ene, etc.

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

Tectonic units from (a); 2 to 60 mole%

Tectonic units from (b); 40 to 98 mole%

More ideally,

Tectonic units from (a); 10 to 50 mol%

Tectonic unit from (b); 50 to 90 mole%

More ideal.

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

Resin [K1], for example, refer to the article "Polymer Synthetic The method described in "Experimental Methods" (by Otsu Takayuki, Issuing Office (Chemical Co., Ltd.), 1st edition, 1st issue, March 1, 1972) and the citations described in this document.

Specifically, for example, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction container, and for example, a method in which nitrogen is substituted for oxygen and heated and held in a deoxygenated environment while stirring. In addition, the polymerization initiator and solvent used here are not particularly limited, and ordinary users in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), and the like, and organic peroxides. (Benzyl peroxide, etc.), as long as it can dissolve each monomer as a solvent, For example, the solvent etc. which are the solvent (E) of the coloring curable resin composition of this invention mentioned later are mentioned.

In addition, the obtained copolymer may be used directly after the reaction, a concentrated or diluted solution may be used, or a solid (powder) may be 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 solution after the reaction can be directly used for the preparation of the colored curable resin composition of the present invention. The manufacturing process of the coloring curable resin composition of this invention is simplified.

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

Tectonic unit from (a); 2 to 45 mole%

Tectonic units from (b); 2 to 95 mole%

Tectonic unit from (c); 1 to 65 mole%

More ideally,

Tectonic unit from (a); 5 to 40 mole%

Tectonic unit from (b); 5 to 80 mole%

Building blocks from (c); 5 to 60 mole%

More ideal.

When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the colored curable resin composition, the developability when a colored pattern is formed, and the solvent resistance, heat resistance, and heat resistance of the obtained color filter The tendency for good mechanical strength.

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

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

Tectonic units from (a); 2 to 60 mole%

Tectonic unit from (c); 40 to 98 mole%

More ideally,

Tectonic units from (a); 10 to 50 mol%

Tectonic unit from (c); 50 to 90 mole%

More ideal.

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

For the resin [K4], a copolymer of (a) and (c) can be obtained, and a cyclic ether having 2 to 4 carbon atoms in (b) can be added to the carboxylic acid and / or (a). Or carboxylic anhydride.

First, the copolymer of (a) and (c) was manufactured by the method similar to the method described as the manufacturing method of resin [K1]. In this case, the ratio from each structural unit is preferably the same ratio as the resin [K3].

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

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

The amount of (b) used is preferably 5 to 80 mol, and more preferably 10 to 75 mol for (a) 100 mol. Within this range, there is a tendency that the balance between 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 obtained color filter will be improved. . Since the cyclic ether has high reactivity and does not easily leave unreacted (b), (b) used in the resin [K4] is preferably (b1) and more preferably (b1-1).

The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b), and (c). The use amount of the 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 and the amount of heat generated by polymerization. In addition, similar to the polymerization conditions, manufacturing equipment, The amount of heat and the like are appropriately adjusted to the feeding method and the reaction temperature.

Resin [K5] was obtained as the first stage in the same manner as in the method for producing the resin [K1], and a copolymer of (b) and (c) was obtained. In the same manner as described above, the obtained copolymer may be used directly after the reaction, a concentrated or diluted solution, or a solid (powder) obtained by a method such as reprecipitation.

The ratios of the structural units derived from (b) and (c) are respectively in terms of the total moles of all the structural units constituting the copolymer.

Building blocks from (b); 5 to 95 mole%

Building blocks from (c); 5 to 95 mole%

More ideally,

Tectonic units from (b); 10 to 90 mole%

Tectonic unit from (c); 10 to 90 mole%

More ideal.

In addition, under the same conditions as in the method for producing the resin [K4], the cyclic ether derived from (b) in the copolymer of (b) and (c) was subjected to the carboxylic acid of (a). The resin [K5] can be obtained by reacting with carboxylic anhydride.

The amount of (a) to be reacted with the copolymer is preferably 5 to 80 moles for (b) 100 moles. Since the cyclic ether has high reactivity and does not easily leave unreacted (b), (b) used in the resin [K5] is preferably (b1), and more preferably (b1-1).

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

Examples of the carboxylic acid anhydride include 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] heptane- 2-ene anhydride and the like. The amount of the carboxylic acid anhydride used is preferably 0.5 to 1 mole for the amount of (a) used as 1 mole.

Specific examples of the resin (B) include 3,4-epoxycyclohexyl methyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxy tricycloacrylic acid [5.2.1.0 ^{2, 6} ] Resins such as decyl ester / (meth) acrylic copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, (meth) Glycidyl acrylate / styrene / (meth) acrylic copolymer, 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decyl / (meth) acrylic acid / N-cyclohexyl maleate Resin [K2]; (methyl) copolymers such as fluorene imine copolymer, 3-methyl-3- (meth) acryloxymethyloxetane / (meth) acrylic acid / styrene copolymer; Resin [K3] such as benzyl acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer; Base) resin added with glycidyl acrylate, resin based on tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer added with (meth) acrylic acid acrylate, Tricyclodecyl methacrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer makes ( Resin [K4], such as acrylic acid propylene acrylate addition resin; Resin that reacts with (meth) acrylic acid in a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate Resins, such as resins for which (meth) acrylic acid reacts with a copolymer of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate [K5]; A resin [K6], such as a cyclodecyl ester / glycidyl (meth) acrylate copolymer, a resin that reacts (meth) acrylic acid, and a resin that reacts with tetrahydrophthalic anhydride. Among them, the resin (B) is preferably a resin [K1] and a resin [K2].

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

The 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. Here, the acid value is a value obtained by measuring the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and is obtained by, for example, titration using an aqueous potassium hydroxide solution.

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

[3] Polymerizable compound (C)

The polymerizable compound (C) is a polymer produced by a polymerization initiator (D). Compounds which can be polymerized by a radical and / or an acid, such as a compound having a polymerizable ethylenically unsaturated bond, are more preferably a (meth) acrylate compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri (meth) acrylate, neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, and dinepentaerythritol. Penta (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, trinepentaerythritol octa (meth) acrylate, trinepentaerythritol hepta (meth) acrylate, tetraneopenta Tetraol deca (meth) acrylate, Tetranepentaerythritol Nine (meth) acrylate, Tris (2- (meth) acryloxyethyl) isocyanurate, Glycol modified new Pentaerythritol tetra (meth) acrylate, ethylene glycol modified dinepentaerythritol hexa (meth) acrylate, propylene glycol modified neopentaerythritol tetra (meth) acrylate, propylene glycol modified dinepentyl Tetraol hexa (meth) acrylate, caprolactone-modified neopentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like.

Among them, dinepentaerythritol penta (meth) acrylate and dinepentaerythritol hexa (meth) acrylate are preferred.

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

The content ratio of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% with respect to the total amount of the solid content of the colored curable resin composition. quality%. When the content ratio of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming the colored pattern and the solvent resistance of the color filter are improved. Propensity.

[4] Polymerization initiator (D)

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating active radicals, acids, and the like by the action of light and heat, and conventional polymerization initiators can be used. Examples of the polymerization initiator that generates living radicals include alkyl phenone compounds, triazine compounds, fluorenylphosphine oxide compounds, O-fluorenyl oxime compounds, and bisimidazole compounds.

The O-fluorenyl oxime compound is a compound having a structure represented by formula (d1). In the following, * indicates a bond key.

Examples of the O-fluorenyl oxime compound include N-benzyloxy-1- (4-phenylhydrothiophenyl) butane-1-one-2-imine and N-benzyloxy -1- (4-phenylhydrothiophenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylhydrothiophenyl) -3- Cyclopentylpropane-1-one-2-imine, N-ethoxyl-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl ] Ethane-1-imine, N-ethoxyl-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxa Cyclopentylmethyloxy) benzylidene} -9H-carbazol-3-yl] ethane-1-imine, N-acetamidooxy-1- [9-ethyl-6- (2 -Methylbenzyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzyloxy-1- [9-ethyl-6- ( 2-methylbenzylidene) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one-2-imine and the like. Commercial products such as Irgacure OXE 01, OXE 02 (above BASF (stock)), N-1919 ((stock) ADEKA), etc. can also be used. Of which, O-fluorenyl oxime The compound is preferably selected from N-benzyloxy-1- (4-phenylhydrothiophenyl) butane-1-one-2-imine and N-benzyloxy-1- (4-phenylhydrothiophenyl) octane-1-one-2-imine and N-benzyloxy-1- (4-phenylhydrothiophenyl) -3-cyclopentyl At least one group of propane-1-one-2-imines, more preferably N-benzyloxy-1- (4-phenylhydrothiophenyl) octan-1-one-2 -Imine. If it is such an O-fluorenyl oxime compound, a high-color color filter tends to be obtained.

The alkyl phenone 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 a compound having a structure represented by formula (d2), for example, 2-methyl-2- (N-morpholinyl) -1- (4-methylhydrothiophenyl) propane-1-one, 2-di Methylamino-1- (4-morpholinylphenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one and the like. Commercial products such as Irgacure 369, 907, and 379 (made by the above BASF (stock)) can also be used.

Examples of compounds having a structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxy Ethoxy) phenyl] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one oligomerization Compounds, α, α-diethoxyacetophenone, benzyldimethylketal, etc.

At the point of sensitivity, as an alkyl phenone compound, It is preferable that it is a compound which has a structure represented by Formula (d2).

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, and 2,4-bis (trichloromethyl) ) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperyl-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 and the like.

Examples of the aforementioned fluorenylphosphine oxide compound include 2,4,6trimethylbenzylfluorenyldiphenylphosphine oxide and the like. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF) can also be used.

Examples of the aforementioned bisimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole and 2,2'-bis (2,3-dichloro (Phenyl) -4,4 ', 5,5'-tetraphenylbisimidazole (refer to Japanese Patent Application Laid-Open No. 6-75372, Japanese Patent Application 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) Phenyl) bisimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (dialkoxyphenyl) bisimidazole, 2,2'-bis (2- (Chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) bisimidazole (refer to Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc.), 4 , An imidazole compound in which a phenyl group at the 4 ', 5,5'-position is substituted with a carbonylalkoxy group (see Japanese Patent Application Laid-Open No. 7-10913, etc.) and the like.

Moreover, 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-benzyl Methyl benzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetrakis (3rd butyl peroxide (Carbonyl) benzophenone compounds such as benzophenone, 2,4,6-trimethylbenzophenone; quinones such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone Compounds; 10-butyl-2-chloroacridone, diphenylethylene dione, methyl phenylglyoxylate, titanocene compounds and the like. These are preferably used in combination with a polymerization initiation aid (D1) (in particular, an amine compound) described later.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethenyloxyphenyldimethyl. Thionium p-toluenesulfonate, 4-Ethyloxyphenyl, methyl, benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexa Onium salts such as fluoroantimonate, diphenylphosphonium p-toluenesulfonate, diphenylphosphonium hexafluoroantimonate, nitrobenzyltoluenesulfonate, benzoin tosylate, and the like.

As the polymerization initiator (D), it is preferred to include at least one group selected from the group consisting of alkyl phenone compounds, triazine compounds, fluorenylphosphine oxide compounds, O-fluorenyl oxime compounds, and bisimidazole compounds The initiator is more preferably a polymerization initiator containing an O-fluorenyl oxime compound.

The content of the polymerization initiator (D) is preferably from 0.1 to 30 parts by mass and more preferably from 1 to 20 parts by mass with respect to 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 higher sensitivity, so the productivity of the color filter is improved.

[5] Polymerization initiation aid (D1)

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

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamine Isoamyl benzoate, 2-dimethylamino ethyl benzoate, 2-ethylhexyl 4-dimethylamino benzoate, 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) Group) benzophenone and the like, and among them, 4,4'-bis (diethylamino) benzophenone is more preferable. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

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

Examples of the aforementioned xanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioanthrone Ketones, 1-chloro-4-propoxythioxanthone and the like.

Examples of the carboxylic acid compound include phenylhydrothioacetic acid, methylphenylhydrothioacetic acid, ethylphenylhydrothioacetic acid, methylethylphenylhydrothioacetic acid, and dimethylphenylhydrothioacetate. Acetic acid, methoxyphenylhydrothioacetic acid, dimethoxyphenylhydrothioacetic acid, chlorophenylhydrothioacetic acid, dichlorophenylhydrothioacetic acid, N-phenylglycine, benzene Hydroxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

When such a polymerization initiation aid (D1) is used, its content is preferably 0.1 to 30 parts by mass, and 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 at a higher sensitivity, and the productivity of a color filter tends to be improved.

[6] Constitution pigment (P)

The colored curable resin composition 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 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 such as zinc oxide (ZnO), titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), zirconia (ZrO ₂ ), and barium carbonate ( BaCO ₃ ), calcium carbonate (CaCO ₃ ), basic magnesium carbonate (MgCO ₃ ), aluminum hydroxide (Al (OH) ₃ ), kaolin, nepheline syenite, and other physical pigments.

Among them, from the viewpoints of solvent resistance, heat resistance, and the like, the extender pigment (P) is more preferably selected from the group consisting of zinc oxide, titanium oxide, silica, zirconia, barium carbonate, calcium carbonate, and basic magnesium carbonate. At least one kind of SiO 2 is more preferably at least one kind selected from the group consisting of zinc oxide, titanium oxide, silicon oxide, and zirconia. Furthermore, in order to obtain a composition capable of producing a color filter with high brightness, among these, a high transparency is preferred. The extender pigment (P) is more preferably a primary particle diameter of 0.1 μm or less, and more preferably 0.05 μm or less, from the viewpoint of high transparency. The primary particle diameter of the extender pigment (P) is usually 0.01 μm or more.

The content ratio of the extender pigment (P) is preferably 0.5 to 10% by mass, more preferably 1 to 7% by mass, and even more preferably 1.5 to 5% by mass of 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 this 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 -COO- in the molecule), ether ester solvents (molecule containing -COO- and -O-solvent), ketone solvent (solvent containing -CO- but not -COO- in the molecule), alcohol solvent (solvent containing OH but not -O-, -CO- and -COO-) , Aromatic hydrocarbon solvents, amine solvents, Dimethyl sulfene and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, and propyl Butyl ester, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, cyclohexanol Acetate and γ-butyrolactone.

Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol. 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, phenyl ether and methyl anisole.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-methoxypropionate. , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy Ethyl-2-methylpropanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl Ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.

Examples of ketone solvents include 4-hydroxy-4-ethyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2-pentanone , Cyclopentanone, cyclohexanone and isophorone.

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

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

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

Among the solvents described above, organic solvents having a boiling point of 1 atm and a boiling point of 120 ° C. or higher and 180 ° C. or lower are preferred from the viewpoints of coating properties and drying properties. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethyl ether are preferred. Diethylene 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 with respect to the total amount of the colored curable resin composition of the present invention. In other words, the total amount of the 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 during coating is improved, and the color density is not insufficient when forming a color filter. Therefore, the display characteristics tend to be improved.

[8] Leveling agent (F)

The colored curable resin composition of the present invention may further contain a leveling agent (F). Examples of the leveling agent (F) include (without a fluorine atom) a polysiloxane-based surfactant, a fluorine-based surfactant, and a polysiloxane-based surfactant having a fluorine atom. These may have a polymerizable group in a side chain.

Examples of the polysiloxane-based surfactant (without a fluorine atom) include a surfactant having a siloxane bond in the molecule. Specifically, for example, TORAY SILICONE DC3PA, the same as SH7PA, the same as DC11PA, the same as SH21PA, the same as SH28PA, the same as SH29PA, the same as SH30PA, and the same as SH8400 (trade name: TORAY‧DOW CORNING (share) system), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (made by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (made by Momentive Performance Materials Japan).

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specifically, for example, FLUORAD (registered trademark) FC430, same FC431 (Sumitomo 3M (shares) system), Megafac (registered trademark) F142D, same F171, same F172, same F173, same F177, same F183, same F554, same R30, Same as RS-718-K (DIC (share) system), EFTOP (registered trademark) EF301, same EF303, same EF351, same EF352 (Mitsubishi Materials Electronics Corporation (share)), SURFLON (registered trademark) S381, same as S382, Same as SC101, same as SC105 (made by Asahi Glass), and E5844 (made by Daikin Institute of Precision Chemistry) 制) and so on.

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

The content of the leveling agent (F) is more 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, and more preferably 0.01 mass% or more and 0.05 mass% or less. It should be noted that the pigment dispersant is not included in the content ratio. 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 coloring curable resin composition of the present invention may further include conventional additives in the technical field such as other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents and the like, as necessary.

<Manufacturing method of colored curable resin composition>

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

The lake pigment is mixed with a part or all of the solvent (E) in advance until the average particle diameter of the colored pigment is about 0.2 μm or less. Dispersion using a ball mill is preferred. In this case, a part or all of the pigment dispersant and the resin (B) may be blended as necessary. In the case where the colorant (A) further contains a coloring pigment, it is preferable to prepare a dispersion liquid of the coloring pigment in the same manner as the dispersion liquid of the lake pigment.

The extender pigment (P) is preferably mixed with a part or all of the solvent (E) in advance, and is preferably dispersed using a ball mill or the like. The color pigment and the extender pigment (P) may be mixed and dispersed at the same time. The pigment dispersion liquid thus obtained can be mixed with the remaining components to a predetermined concentration to prepare the intended colored curable resin composition.

When the colorant (A) contains a dye, the solution can be prepared by dissolving a part or all of the solvent (E) separately in advance. This solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.

The mixed colored curable resin composition is preferably filtered with a filter having 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 a color filter. A color filter formed from the coloring curable resin composition of the present invention is also one aspect of the present invention.

The color filter of the present invention may include a step of applying the coloring curable resin composition to a substrate, drying it to form a coloring composition layer, and curing the coloring composition layer by exposure. Method formation. The color filter of the present invention has a colored pattern and a colored coating film.

Specific methods for producing a colored pattern include, for example, a lithography method, an inkjet method, and a printing method. Among them, the lithography method is preferable. The lithography method is a method in which the colored curable resin composition is coated on a substrate and dried to form a colored composition layer. The colored composition layer is exposed and developed through a photomask. In the lithography method, a colored coating film of a cured product of the coloring composition layer described above can be formed without using a mask and / or no development during exposure.

The film thickness of the color filter of the present invention is not particularly limited and may be appropriately adjusted depending on the purpose, use, and the like, for example, 0.1 to 30 μm, more preferably 0.1 to 20 μm, and even more preferably 0.5 to 6 μm.

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

The formation of each color pixel by the lithography method can be performed by a conventional or conventional device and conditions. For example, it is produced as follows.

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

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

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

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

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

Then, the colored composition layer is exposed through a mask for forming a desired colored pattern. The pattern on the reticle is not particularly limited, and a pattern depending on the purpose can be used.

As a light source used for the exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, for light less than 350 nm, a filter that cuts off the wavelength region is used to cut off, or light near 436 nm, 408 nm, and 365 nm is selectively extracted using a band-pass filter that takes out the wavelength region. Specifically, for example, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, and the like.

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

The coloring composition layer after exposure is brought into contact with a developing solution, and development is performed to form a coloring pattern on the substrate. By the development, the unexposed part of the colored composition layer is dissolved in the developing solution and removed. As the developing solution, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide, or the like is preferable. The concentration of such an alkaline compound in an aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. Furthermore, the developing solution may contain a surfactant.

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

Moreover, it is preferable to perform post-baking on the obtained 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 having excellent heat resistance and solvent resistance can be produced. This color filter can be used as a color filter used in a display device (a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state imaging element.

[Example]

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

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

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

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

The following reactions were performed under a nitrogen atmosphere. Into a flask equipped with a cooling tube and a stirring device, 8 parts of the compound represented by the above formula (A-II-18) and 396 parts of methanol were charged, followed by stirring at room temperature for 30 minutes to prepare a blue solution. Then, 396 parts of water was added to the blue solution, and then stirred at room temperature for 30 minutes to obtain a reaction solution.

53 parts of water was put into a beaker, and then 11.8 parts of Keggin structure type phosphotungstic acid (manufactured by Aldrich) and 53 parts of methanol were put into the water, and they were mixed in an air environment 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 at room temperature for 30 minutes, 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 under reduced pressure at 60 ° C to obtain 17.1 parts of a compound [lake pigment (A1)] represented by the formula (A-I-18).

<Preparation of dispersion liquid>

14 parts of a compound represented by the formula (AI-18), 2.5 parts of a dispersant (BYK (registered trademark) -LPN6919 (BYK-Chemie Japan)), 6 parts of a resin (B1) (equivalent solid content), and 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 dibenzopiperan dye (A2)>

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

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

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

Then, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ester, and / or 3,4-epoxytricyclo [5.2] .1.0 A mixed solution of 289 parts 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 added dropwise over 6 hours. After the dropwise addition, the resin was maintained at the same temperature for 4 hours and then cooled to room temperature to obtain a resin (B1) having a B-type 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 weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured using the GPC method under the following conditions.

Installation; K2479 (made by Shimadzu Corporation)

Column; 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 (manufactured by TOSOH).

The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the converted polystyrene 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 amount of each component in Table 1 is "mass part". As will be described later, regarding the lake pigment (A1) and the extender pigments (P1) to (P4), a dispersant, a resin (B1), and a solvent (E1) or (E4) are mixed in advance to be used as a dispersion liquid for coloring. The preparation of a curable resin composition is shown in Table 1, and shows the content of each component contained in the coloring curable resin composition finally obtained. The numerical value of Table 1 is the solid content amount (mass part) of each component.

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

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

In addition, in Table 1, each component is as follows. The resin (B1) represents a mass part in terms of solid content.

[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] Polymerizable compound (C1): dipentaerythritol 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 ; Manufactured by BASF; oxime compounds)

[6] Constitution pigment dispersion (P1): zinc oxide dispersion. When preparing the coloring curable resin composition, a dispersion liquid obtained by mixing zinc oxide (10 parts), an acrylic pigment dispersant (1.3 parts), and a solvent (E1) (88.7 parts) shown in Table 1 in advance was used as a formulation. ingredient.

[7] An extender pigment dispersion (P2): a titanium oxide dispersion. When preparing the coloring curable resin composition, a dispersion liquid obtained by mixing in advance titanium oxide (10 parts), an acrylic pigment dispersant (3 parts), and a solvent (E1) (87 parts) shown in Table 1 was used as a formulation. ingredient.

[8] Constitution pigment dispersion (P3): silica dispersion (PGM-AC-0413; manufactured by Nissan Chemical Industries, Inc., containing 30% constitution pigment)

[9] Constitution pigment dispersion (P4): zirconia dispersion (SZR; manufactured by Sakai Chemical Co., Ltd., containing 30% constitution pigment)

[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 5 cm square glass substrate (EAGLE2000; manufactured by Corning), a colored hardening resin composition was applied by a spin coating method so that the post-baking film thickness was 2 μm, and then pre-baked at 100 ° C. for 3 minutes to form Coloring composition layer. After leaving to cool, the colored composition layer was irradiated with light using an exposure machine (TME-150RSK; manufactured by TOPCON) in an atmospheric environment with an exposure amount of 150 mJ / cm ² (based on 365 nm). After light irradiation, post-baking was performed at 230 ° C. for 20 minutes in an oven to obtain a colored coating film.

(3) Chroma evaluation

With respect to the obtained colored coating film, a colorimeter (OSP-SP-200; manufactured by OLYMPUS) was used to measure the spectrometer, and a characteristic function of a C light source was used to measure the xy chromaticity coordinates (x, y) and stimulus value Y. A larger value of Y indicates higher brightness. The results are shown in Table 2.

(4) Evaluation of heat resistance

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

(5) Evaluation of solvent resistance

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

<Comparative Example 2>

(A) colorant; mixed

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

15 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 198 parts

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

(A) Dispersion liquid (A1); 82 parts of dispersion liquid (1)

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

(C) Polymerizable compound; (C-1) 50 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D) Polymerization initiator; (D-1); N-benzyloxy-1- (4-phenylhydrothiophenyl) octane-1-one-2-imine (registered trademark) ) OXE 01; manufactured by BASF; oxime compound) 14 parts

(F) Leveling agent; (F-1); Polyether modified silicone oil (TORAY SILICONE SH8400; TORAY‧DOW CORNING (shares)) 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.

In accordance with the procedure described in "(2) Preparation of colored coating film", a colored coating film was produced from the obtained colored curable resin composition. About the obtained colored coating film, it carried out similarly to Examples 1-4 and Comparative Example 1, and performed the chromaticity evaluation, heat resistance evaluation, and solvent resistance evaluation. Each result is shown in Table 2.

(Industrial possibility)

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

Claims (6)

A colored hardening resin composition, comprising: a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a constitution pigment (P); wherein the colorant includes a lake pigment. The colored hardening resin composition according to item 1 of the scope of the patent application, wherein the lake pigment is an anion having a compound containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen, and has an Compound (Aa) composed of cations of a pigment skeleton. The colored curable resin composition according to item 2 of the scope of patent application, wherein the aforementioned compound (Aa) is a compound represented by formula (AI), and [X ⁺ ] _m [Y] ^m- (AI) formula (AI) Wherein X ⁺ represents a cation represented by the 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 an arbitrary natural number; and in formula (AIX), R ⁴¹ to R ^{44 are} mutually Independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms which may have a substituent, and an oxygen atom is interposed between the methylene groups constituting the alkyl group (however, plural oxygen atoms do not Inserted adjacently), a monovalent aromatic hydrocarbon group having 6 to 14 carbons which may have a substituent, an aralkyl group or hydrogen atom having 7 to 11 carbons which may have a substituent; R ⁴¹ and R ⁴² may be bonded And form a ring together with the nitrogen atoms bonded to them, R ⁴³ and R ⁴⁴ may be bonded and form a ring together with the nitrogen atoms bonded to them; R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, When a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms has a carbon number of 2 or more, an oxygen atom may be inserted between the methylene groups constituting the alkyl group (but a plurality of oxygen atoms will not be adjacent to each other). Mode insertion); R ⁴⁸ and R ⁵² may be 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; m is 2 or more natural numbers , X ⁺ may be a plurality of the same structure, it may also be differently configured. The colored hardening resin composition according to item 1 or 2 of the scope of the patent application, wherein the constitution pigment (P) is at least one selected from the group consisting of zinc oxide, titanium oxide, silicon oxide, and zirconia. A color filter is formed of a color-hardening resin composition as described in item 1 or 2 of the scope of patent application. A display device includes a color filter as described in item 5 of the scope of patent application.