JP5899981B2 - Colored curable resin composition - Google Patents

Description

  The present invention relates to a colored curable resin composition.

  A display device using a color filter has a problem that the brightness is low because an image is displayed by light transmitted through the color filter, as compared with a self-luminous display device such as a plasma display. In order to obtain a bright and clear image, a color filter with high brightness is required. The color filter is produced from a colored curable resin composition. As such a colored curable resin composition, a zinc phthalocyanine compound and C.I. I. A colored curable resin composition containing Solvent Yellow 162 is known (Patent Document 1).

“This is the whole picture of the display!” P. 114 (by Wataru Izumiya; Kanki Publishing April 18, 2005)

JP 2010-168531 A

  In order to obtain a bright and clear image, a color filter with high brightness is required. Conventionally known colored curable resin compositions as described above may not always satisfy both lightness and solvent resistance.

The present invention provides the following [1] to [7].
[1] includes a colorant, a resin, a polymerizable compound, a polymerization initiator, and a solvent,
A colored curable resin composition, wherein the colorant is a colorant comprising a compound represented by formula (I) and a zinc phthalocyanine compound.

[In Formula (I), Z ¹ , Z ² and L ¹ each independently represent a C 1-16 divalent aliphatic hydrocarbon group which may have a substituent, and the aliphatic —CH ₂ — contained in the hydrocarbon group may be replaced by —CO— or —O—.
R ¹ and R ² are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, or a carbon atom having 2 to 2 carbon atoms which may have a substituent. 18 acyl groups are represented.
A ¹ and A ² each independently represent a C 6-14 divalent aromatic hydrocarbon group which may have a substituent.
B ¹ and B ² are each independently a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a C ^{3 to} 14 carbon group which may have a substituent. A monovalent heterocyclic group is represented, and —CH ₂ — contained in the heterocyclic group may be replaced by —CO—. ]
[2] The colored curable resin composition according to [1], wherein the zinc phthalocyanine compound is a compound represented by the formula (P).

Wherein ^{(P), A} 1 ^{~A 16} each independently represent a hydrogen atom, a chlorine atom or a bromine atom. ]
[3] The colored curable resin composition according to [1] or [2], wherein the colorant is a colorant comprising two or more compounds represented by formula (I) and a zinc phthalocyanine compound.
[4] The colored curable resin composition according to any one of [1] to [3], wherein the colorant is a colorant comprising a compound represented by formula (I) and a zinc phthalocyanine pigment.
[5] The colored curable resin composition according to any one of [1] to [3], wherein the solvent is a solvent containing propylene glycol monomethyl ether.
[6] A color filter formed from the colored curable resin composition according to any one of [1] to [5].
[7] A display device including the color filter according to [6].

  According to the colored curable resin composition of the present invention, a color filter having high brightness and solvent resistance can be formed.

The colored curable resin composition of the present invention includes a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E). Is a colored curable resin composition which is a colorant containing a compound represented by (hereinafter sometimes referred to as “compound (I)”) and a zinc phthalocyanine compound.
The colored curable resin composition of the present invention contains compound (I) as the colorant (A).

[In Formula (I), Z ¹ , Z ² and L ¹ each independently represent a C 1-16 divalent aliphatic hydrocarbon group which may have a substituent, and the aliphatic —CH ₂ — contained in the hydrocarbon group may be replaced by —CO— or —O—.
R ¹ and R ² are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, or a carbon atom having 2 to 2 carbon atoms which may have a substituent. 18 acyl groups are represented.
A ¹ and A ² each independently represent a C 6-14 divalent aromatic hydrocarbon group which may have a substituent.
B ¹ and B ² are each independently a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a C ^{3 to} 14 carbon group which may have a substituent. A monovalent heterocyclic group is represented, and —CH ₂ — contained in the heterocyclic group may be replaced by —CO—. ]

The carbon number of the divalent aliphatic hydrocarbon group having ¹ to 16 carbon atoms representing Z ¹ , Z ² and L ¹ does not include the carbon number of the substituent, and the number is preferably 2 to 10, more preferably Is 2-8.
Examples of the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include a methylene group, an ethylene group, a propanediyl group, a butanediyl group, a pentanediyl group, a hexanediyl group, a heptanediyl group, an octanediyl group, a decandidiyl group, and a tetradecandiyl group. and hexadecane-diyl group having 1 to 16 carbon atoms such as alkanediyl _{group; -CH 2 = CH 2 -,} - CH 2 -C (= CH 2) -, - (CH 2) 2 -C (= CH 2) - C1-C16 alkenediyl groups, such as, etc. are mentioned.
—CH ₂ — contained in the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms may be replaced by —CO— or —O—, and is a divalent aliphatic hydrocarbon having 1 to 16 carbon atoms. The hydrogen atom contained in the group may be substituted with a halogen atom such as a fluorine atom.

As Z ¹ and Z ² , —CH ₂ — is preferably an alkanediyl group having 1 to 8 carbon atoms which may be substituted with —O—, and —CH ₂ — is substituted with —O—. More preferably, it is an alkanediyl group having 5 to 7 carbon atoms. Preferable groups include, for example, — (CH ₂ ) ₃ —, — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ —O— (CH _{2) 2} - and _-CH 2 -CH (CH ₃₎ - and the like.

L ¹ is preferably an alkanediyl group having 1 to 8 carbon atoms which may contain —C (═CH ₂ ) —, and may be an unsubstituted alkanediyl group having 1 to 8 carbon atoms. More preferably, it is an unsubstituted alkanediyl group having 4 to 8 carbon atoms. Preferable groups include, for example, — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, or —CH ₂ —C (═CH ₂ ) —.

The monovalent saturated hydrocarbon group having 1 to 16 carbon atoms representing R ¹ and R ² may be any of linear, branched or cyclic. The carbon number of the saturated hydrocarbon group does not include the carbon number of the substituent, and the number thereof is 1 to 16, preferably 1 to 10, and more preferably 1 to 4.
Examples of the monovalent saturated hydrocarbon group having 1 to 16 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and methylbutyl group. (Such as 1,1,3,3-tetramethylbutyl group), methylhexyl group (such as 1,5-dimethylhexyl group), ethylhexyl group (such as 2-ethylhexyl group), cyclopentyl group, cyclohexyl group, methylcyclohexyl group ( 2-methylcyclohexyl group), cyclohexylalkyl group and the like.
The hydrogen atom contained in the saturated hydrocarbon group may be substituted with an alkoxy group having 1 to 8 carbon atoms or a carboxy group. Examples of the aliphatic hydrocarbon group substituted with an alkoxy group having 1 to 8 carbon atoms include a propoxypropyl group (such as 3-isopropoxypropyl group) and an alkoxypropyl group (such as 3- (2-ethylhexyloxy) propyl group). Etc. Examples of the saturated hydrocarbon group substituted with a carboxy group include a 2-carboxyethyl group, a 3-carboxypropyl group, and a 4-carboxybutyl group.

A hydrogen atom contained in an acyl group having 2 to 18 carbon atoms representing R ¹ and R ² may be substituted with a carboxy group or an alkoxy group having 1 to 8 carbon atoms. Carbon number of this acyl group is counted including carbon number of a substituent, and the number is 2-18, Preferably it is 6-10. Examples of the acyl group that may have a substituent include an acetyl group, a benzoyl group, and a methoxybenzoyl group (such as a p-methoxybenzoyl group).

The R ¹ and R ^2, a hydrogen atom, preferably an alkyl group and an acyl group having 2 to 5 carbon atoms having 1 to 4 carbon atoms, a hydrogen atom, more preferably a methyl group and acetyl group.

Examples of the divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent representing A ¹ and A ² include a phenylene group and a naphthalenediyl group, preferably a phenylene group. . The carbon number of the aromatic hydrocarbon group does not include the carbon number of the substituent.
Examples of the substituent that the aromatic hydrocarbon group may have include a halogeno group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a nitro group, a sulfo group, a sulfamoyl group, and N- Examples thereof include a substituted sulfamoyl group.

  Examples of the halogeno group include a fluoro group, a chloro group, a bromo group, and an iodo group, and a fluoro group, a chloro group, and a bromo group are preferable.

  Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group and hexyl group. A C 1-4 alkyl group is preferred, a methyl group and an ethyl group are more preferred, and a methyl group is particularly preferred.

  Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group and hexyloxy group. An alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group and an ethoxy group are more preferable, and a methoxy group is particularly preferable.

Examples of the N-substituted sulfamoyl group include a —SO ₂ NHR ⁶ group or a —SO ₂ NR ⁶ R ⁷ group. R ⁶ and R ⁷ each independently represents an optionally substituted saturated hydrocarbon group having 1 to 16 carbon atoms or an optionally substituted acyl group having 2 to 16 carbon atoms. . The same thing as the above is mentioned as a C1-C16 saturated hydrocarbon group which may have a substituent, and a C2-C16 acyl group which may have a substituent.

Examples of the monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms representing B ¹ and B ² include a phenyl group and a naphthyl group. The carbon number of the aromatic hydrocarbon group does not include the carbon number of the substituent.
Examples of the monovalent heterocyclic group having 3 to 14 carbon atoms which may have a substituent representing B ¹ and B ² include groups represented by the following formulas.

[R represents a hydrogen atom or an organic group. ]
Examples of the organic group include the same groups as R ⁴ to be described later.
The hydrogen atom contained in the monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms and the monovalent heterocyclic group having 3 to 14 carbon atoms is a hydroxy group, an aliphatic hydrocarbon group having 1 to 16 carbon atoms, or cyano. It may be substituted with a group, amino group or N-substituted amino group. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an oxo group. —CH ₂ — contained in the heterocyclic group may be replaced by —CO—.
Examples of the N-substituted amino group include —NHR ⁸ group and —SO ₂ NR ⁸ R ⁹ group. R ⁸ and R ⁹ are each independently a monovalent C 1-16 aliphatic hydrocarbon group which may have a substituent or a monovalent carbon number 3 which may have a substituent. Represents a heterocyclic group of -14. Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent and the monovalent heterocyclic group having 3 to 14 carbon atoms which may have a substituent include the above-mentioned Examples thereof include the same groups as those described as the heterocyclic group.

B ¹ and B ² are preferably a group represented by the formula (II).

[In Formula (II), R ⁴ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms which may have a substituent.
R ⁵ represents a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms which may have a substituent. ]
The pyridone ring of the group represented by the formula (II) may be keto type or enol type.

Examples of the monovalent saturated hydrocarbon group having 1 to 16 carbon atoms representing R ⁴ and R ⁵ are the same as those described above.
R ⁴ includes a methylbutyl group (such as 1,1,3,3-tetramethylbutyl group), a methylhexyl group (such as 1,5-dimethylhexyl group), and an ethylhexyl group (such as 2-ethylhexyl group). Branched saturated hydrocarbon groups such as a methylcyclohexyl group (such as 2-methylcyclohexyl group) and an alkoxypropyl group (such as 3- (2-ethylhexyloxy) propyl group) are preferable.
R ⁵ is preferably a methyl group.

Examples of compound (I) include compounds represented by formula (I-1) to formula (I-21). A ¹ , A ² , Z ¹ and Z ² in the table represent a bond having the right bond close to L ¹ .

B ¹ and B ² are preferably the same type of group, and more preferably A ¹ and A ² , R ¹ and R ² , and Z ¹ and Z ² are the same type of group, respectively. With these groups, the production of compound (I) is easy.

When the colored curable resin composition of the present invention comprising two or more of the compound (I), the compound (I), ^A 1 in formula ^{(I), A 2, R} 1, R 2, Z 1, Z 2 and at least one is different from the structure from each other compound selected from the group consisting of L ^1, preferably contains two or more, at least one selected from the group consisting of Z ^1, Z ² and L ¹ are different from each other structural It is more preferable to include two or more types of compounds, and it is even more preferable to include two or more types of compounds in which only L ¹ has a different structure.
Especially, it is preferable that the compound represented by Formula (I-6) and the compound represented by Formula (I-7) are included as Compound (I). The ratio of the content of the compound represented by formula (I-6) and the compound represented by formula (I-7) is preferably 10:90 to 89:11, more preferably 30:70 to 70:30. preferable. When the content ratio is within the above range, the compound (I) hardly precipitates in the colored curable resin composition and is excellent in storage stability.

  Content of compound (I) is 0.5-99.5 mass% with respect to coloring agent (A) whole quantity, Preferably it is 1-99 mass%, More preferably, it is 2-98 mass%. is there.

The colored curable resin composition of the present invention contains a zinc phthalocyanine compound as the colorant (A). A zinc phthalocyanine compound is a phthalocyanine compound having zinc as a central metal, and examples thereof include compounds described in JP-A-7-286109, JP-A-2008-24743, and JP-A-2009-51896. The zinc phthalocyanine compound is preferably contained in the colored curable resin composition of the present invention as a zinc phthalocyanine pigment. The zinc phthalocyanine pigment is a pigment containing a zinc phthalocyanine compound, and is preferably a green pigment.
The zinc phthalocyanine compound is preferably a compound represented by the formula (P).

Wherein ^{(P), A} 1 ^{~A 16} each independently represent a hydrogen atom, a chlorine atom or a bromine atom. ]
The number of substituents represented by A ^{1 to} A ¹⁶ is preferably 0 to 6 chlorine atoms, 10 to 16 bromine atoms, and 10 to 16 sum of chlorine and bromine atoms. More preferably, the number of chlorine atoms is 0-3, the number of bromine atoms is 13-16, and the sum of chlorine atoms and bromine atoms is 13-16, and more preferably the number of chlorine atoms is 1. -3, 13-15 bromine atoms, and 14-16 sum of chlorine and bromine atoms.
When the number of substituents is in the above range, the hue becomes yellowish, and the brightness becomes high without lowering the color reproduction range when a color filter is formed.

Examples of the pigment containing the compound represented by the formula (P) include C.I. I. And CI Pigment Green 58.
The compound represented by the formula (P) and the pigment containing the compound are described in publications such as JP2007-284589, JP2007-284592, JP2007-291232, and JP2008-19383. It can be manufactured by the method.

Zinc phthalocyanine pigment is optionally treated by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment on the pigment surface with a polymer compound, sulfuric acid atomization method, etc. Atomization treatment, cleaning treatment with an organic solvent or water for removing impurities, removal treatment by an ion exchange method of ionic impurities, or the like may be performed.
The zinc phthalocyanine pigment preferably has a uniform particle size. A zinc phthalocyanine pigment dispersion in which the zinc phthalocyanine pigment is uniformly dispersed in the solution can be obtained by adding a pigment dispersant to the dispersion treatment.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by CIBA), Ajispur (Ajinomoto Fine) (Techno Co., Ltd.), Disperbyk (Bic Chemie) and the like.
When the pigment dispersant is used, the amount used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, with respect to 100 parts by mass of the zinc phthalocyanine pigment. When the amount of the pigment dispersant used is in the above range, there is a tendency that a zinc phthalocyanine pigment dispersion in a uniform dispersion state can be obtained.

  Content of a zinc phthalocyanine compound is 0.5-99.5 mass% with respect to the whole quantity of a coloring agent (A), Preferably it is 1-99 mass%, More preferably, it is 2-98 mass%. is there.

The colored curable resin composition of the present invention may contain a dye and / or pigment different from the compound (1) and the zinc phthalocyanine compound as the colorant (A).
Examples of the dye different from the compound (1) and the zinc phthalocyanine compound include oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamides of acid dyes. For example, color index (The Society of Dyers and Colourists publication) dyes, that is, compounds classified as having a hue other than pigments, and known dyes described in dyeing notes (color dyeing company). In addition, according to the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, and the like can be given. Of these, organic solvent-soluble dyes are preferred.

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

Examples of the pigment different from the compound (1) and the zinc phthalocyanine compound include organic pigments such as C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as 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;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7 and 36;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.
These pigments may be used alone or in combination of two or more.

  Among them, C.I. I. Pigment yellow 138, 139, 150 and C.I. I. Pigment Green 7 and 36 are preferable.

If necessary, the above pigment may be obtained by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment on the pigment surface with a polymer compound, sulfuric acid atomization method, etc. The above-mentioned pigment may be subjected to atomization treatment, washing treatment with an organic solvent or water for removing impurities, removal treatment by ion exchange method of ionic impurities, and the like. It is preferable to perform the dispersion process in the same manner.

  In the colorant (A), the content ratio between the compound (I) and the zinc phthalocyanine compound is preferably 1:99 to 35:65, more preferably 10:90 to 30:70, based on mass. The colorant (A) may contain a dye and / or pigment different from the compound (1) and the zinc phthalocyanine compound, but it is preferable that the colorant (A) does not substantially contain it. By using such a colorant (A), a high brightness color filter can be produced.

  The content of the colorant (A) is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and still more preferably based on the solid content of the colored curable resin composition of the present invention. It is 10-50 mass%. When the content of the colorant (A) is within the above range, the color density when it is used as a color filter is sufficient, and the resin (B) and the polymerizable compound (C) are contained in a necessary amount in the composition. Therefore, a colored pattern with sufficient mechanical strength can be formed. Here, solid content means the total amount of the component remove | excluding the solvent from the colored photosensitive resin composition of this invention. The solid content and the content of each component relative thereto can be measured by a known analysis means such as liquid chromatography or gas chromatography.

The colored curable resin composition of the present invention contains a resin (B). Although it does not specifically limit as resin (B), It is preferable that it is alkali-soluble resin.
Examples of the resin (B) include the following resins [K1] to [K4].
[K1] a monomer (a) having a C2-C4 cyclic ether structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(a)"), an unsaturated carboxylic acid and an unsaturated carboxylic acid A copolymer with at least one (b) selected from the group consisting of anhydrides (hereinafter sometimes referred to as “(b)”).
[K2] (a), (b), and monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter referred to as “(c)”) [K3] Copolymer of (b) and (c) [K4] A resin obtained by reacting (a) with a copolymer of (b) and (c).
By including the structural unit derived from (a) in the resin (B), the obtained color filter can have higher reliability such as heat resistance and chemical resistance.

(A) is, for example, a polymerizable compound having a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Say. (A) is preferably a monomer having a C2-C4 cyclic ether structure and a (meth) acryloyloxy group.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  Examples of (a) include a monomer (a1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(a1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (a2) (hereinafter sometimes referred to as “(a2)”), monomer (a3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(a3)”), and the like Can be mentioned.

  (A1) is, for example, a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, an ethylenically unsaturated bond, and a monomer (a1-1) (hereinafter referred to as “(a1-1) And a monomer (a1-2) having an epoxidized structure of an alicyclic unsaturated hydrocarbon, an ethylenically unsaturated bond and a structure (hereinafter referred to as “(a1-2)”) There are).

  As (a1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6- Examples include tris (glycidyloxymethyl) styrene.

  Examples of (a1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate ( For example, cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), and represented by formula (B1) Examples thereof include compounds and compounds represented by formula (B2).

[In Formula (B1) and Formula (B2), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group May be substituted.
X ^a and ^{X b} are each independently a single ^{bond, -R c -, * - R} c -O -, * - R c -S -, * - represents the R c -NH-.
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy Examples include a -1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
R ^a and R ^b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- Examples include 1,6-diyl group.
X ^a and X ^b are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— (* represents a bond to O) group, or * —CH ₂ CH ₂ —O— group. More preferably, a single bond and a * —CH ₂ CH ₂ —O— group are mentioned.

  Examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to the formula (I-15). Preferably Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9) or Formula (I-11) to Formula (I-15) The compound represented by these is mentioned. More preferably, the compound represented by Formula (I-1), Formula (I-7), Formula (I-9) or Formula (I-15) is mentioned.

  Examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to the formula (II-15). Preferably Formula (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula (II-9) or Formula (II-11) to Formula (II-15) The compound represented by these is mentioned. More preferably, the compound represented by Formula (II-1), Formula (II-7), Formula (II-9), or Formula (II-15) is mentioned.

  The compound represented by the formula (B1) and the compound represented by the formula (B2) can be used alone. They can also be mixed in any ratio. In the case of mixing, the mixing ratio is molar ratio, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, particularly preferably 20:80 in the formula (B1): formula (B2). ~ 80: 20.

  As the monomer (a2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. As (a2), 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane , 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

As the monomer (a3) having a tetrahydrofuryl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable.
Specific examples of (a3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

  (A) is preferably (a1) in that the reliability of the obtained color filter such as heat resistance and chemical resistance can be further increased. Furthermore, (a1-2) is more preferable in that the storage stability of the colored curable resin composition is excellent.

Specific examples of (b) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;

Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in the art, it is referred to as dicyclopentanyl (meth) acrylate as a common name), dicyclopentanyloxyethyl (meth) acrylate, tricyclo [5.2 (In the art, as trivial names are said dicyclopentenyl (meth) acrylate.) 1.0 ^2,6] decene-8-yl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) (Meth) acrylic esters such as acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;

  Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2. .1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Bicyclo unsaturated compounds;

  N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Among these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and heat resistance. preferable.

In the resin [K1], the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K1].
Structural unit derived from (a); 50 to 98 mol% (more preferably 60 to 90 mol%)
Structural unit derived from (b); 2 to 50 mol% (more preferably 10 to 40 mol%)
When the ratio of the structural unit of the resin [K1] is within the above range, the storage stability and developability of the colored photosensitive resin composition and the solvent resistance of the color filter tend to be good.

  The resin [K1] is, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and the document Can be produced with reference to the cited references described in 1.

  Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, for example, by substituting oxygen with nitrogen to create a deoxygenated atmosphere while stirring. The method of heating and keeping warm is exemplified. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and any of those usually used in the field can be used. For example, as polymerization initiators, azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) Any solvent may be used as long as it dissolves each monomer, and a solvent described later can be used as the solvent (E) of the colored photosensitive resin composition of the present invention.

  In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using the solvent contained in the colored photosensitive resin composition of the present invention as a solvent in the polymerization, the solution after the reaction is used as it is for the preparation of the colored photosensitive resin composition of the present invention. Therefore, the manufacturing process of the colored photosensitive resin composition of the present invention can be simplified.

In the resin [K2], the ratio of the structural units derived from each is preferably within the following range among all the structural units constituting the resin [K2].
Structural unit derived from (a); 2-95 mol% (more preferably 5-80 mol%)
Structural unit derived from (b); 4-45 mol% (more preferably 10-30 mol%)
Structural unit derived from (c); 1 to 65 mol% (more preferably 5 to 60 mol%)
When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability and developability of the colored photosensitive resin composition, and the solvent resistance, heat resistance and mechanical strength of the color filter are improved. Tend.

Resin [K2] can be produced, for example, in the same manner as the method described as the production method of resin [K1].
Specifically, a predetermined amount of (a), (b) and (c), a polymerization initiator and a solvent are placed in a reaction vessel, for example, by substituting oxygen with nitrogen to form a deoxygenated atmosphere, A method of heating and keeping warm while stirring is mentioned. As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation. May be used.

In the resin [K3], the ratio of the structural unit derived from each is preferably in the following range among all the structural units constituting the resin [K3].
(B) 2 to 50 mol%, more preferably 5 to 40 mol%
(C) 50 to 98 mol%, more preferably 60 to 95 mol%
Resin [K3] can be produced, for example, in the same manner as described for the production method of resin [K1].

Resin [K4] can be obtained by obtaining a copolymer of (b) and (c) and adding (a).
First, a copolymer of (b) and (c) is produced in the same manner as the method described as the production method of [K1]. In this case, the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the copolymer of (b) and (c).
(B) 5 to 50 mol%, more preferably 10 to 45 mol%
(C) 50 to 95 mol%, more preferably 55 to 90 mol%
Next, the carboxy group and / or part of the carboxylic acid anhydride contained in the structural unit derived from (b) in the copolymer is reacted with a C2-C4 cyclic ether of (a). .
Subsequent to the production of the copolymer of (b) and (c), the atmosphere in the flask is replaced by nitrogen to air, and (a) a reaction catalyst of a carboxy group and a cyclic ether (for example, tris (dimethylaminomethyl) phenol Etc.), a polymerization inhibitor (for example, hydroquinone, etc.) and the like are placed in a flask and reacted at 60 to 130 ° C. for 1 to 10 hours, for example, to obtain the resin [K4]. The usage-amount of the said reaction catalyst is 0.001-5 mass% normally with respect to the total amount of (a)-(c). The usage-amount of the said polymerization inhibitor is 0.001-5 mass% normally with respect to the total amount of (a)-(c). The reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization.
In this case, the amount of (a) used is preferably from 5 to 80 mol%, more preferably from 10 to 75 mol%, and even more preferably from 15 to 70 mol%, based on (b). By setting it as this range, there exists a tendency for the balance of the storage stability of a colored photosensitive resin composition, developability, and sensitivity, color filter solvent resistance, heat resistance, and mechanical strength to become favorable.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6. ] Resin such as decyl acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meta ) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6] decyl acrylate / methacrylic acid / vinyl toluene copolymer, 3-methyl-3- (meth) acrylic Roy Resin such as oxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, vinyltoluene / Resin such as methacrylic acid copolymer [K3]; resin obtained by adding glycidyl (meth) acrylate to benzyl (meth) acrylate / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / styrene / (meta ) Resin with glycidyl (meth) acrylate added to acrylic acid copolymer, glycidyl (meth) acrylate added to tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer Examples thereof include resin [K4] such as resin. Among them, resin [K1] and resin [K2] are preferable, resin [K1] is more preferable, and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid co-polymer. More preferred are polymers.

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 35,000. Particularly preferred is 6,000 to 30,000, and particularly preferred is 7,000 to 28,000. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film ratio is high, the solubility of the unexposed portion in the developer is good, and the resolution tends to be improved.
The molecular weight distribution [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 150 mg-KOH / g, more preferably 60 to 135 mg-KOH / g, and still more preferably 70 to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin, and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

  Content of resin (B) becomes like this. Preferably it is 7-65 mass% with respect to solid content of the colored curable resin composition of this invention, More preferably, it is 13-60 mass%, More preferably, it is 17 It is -55 mass%. When the content of the resin (B) is in the above range, the resolution of the coloring pattern and the remaining film ratio tend to be improved.

  The colored curable resin composition of the present invention contains a polymerizable compound (C). The polymerizable compound (C) is a compound that can be polymerized by active radicals and acids generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond. (Meth) acrylic acid ester compound is mentioned.

Among these, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octane. (Meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified penta Erythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol Le-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate. Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like can be given. The polymerizable compounds may be used alone or in combination of two or more.
The weight average molecular weight of the polymerizable compound (C) is preferably from 150 to 2,900, more preferably from 250 to 1,500.

  The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, based on the solid content of the colored curable resin composition of the present invention. Preferably it is 17-55 mass%. When the content of the polymerizable compound (C) is within the above range, the curing is sufficiently performed, the remaining film ratio in the development is improved, and the undercut is difficult to enter into the colored pattern, so that the adhesion is improved. This is preferable because it tends to be good.

The colored curable resin composition of the present invention contains a polymerization initiator (D).
The polymerization initiator (D) is not particularly limited as long as it is a compound that generates an active radical, an acid, etc. by the action of light or heat and can initiate polymerization, and a known polymerization initiator is used. Can do.
As the polymerization initiator (D), a compound that generates an active radical by the action of light is preferable, and an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an oxime compound, and a biimidazole compound are more preferable.

式（ｄ２）で表される部分構造を有する化合物としては、例えば、２−メチル−２−モルホリノ−１−（４−メチルスルファニルフェニル）プロパン−１−オン、２−ジメチルアミノ−１−（４−モルホリノフェニル）−２−ベンジルブタン−１−オン、２−（ジメチルアミノ）−２−［（４−メチルフェニル）メチル］−１−［４−（４−モルホリニル）フェニル］ブタン−１−オン等が挙げられる。イルガキュア（登録商標）３６９、９０７及び３７９（以上、ＢＡＳＦ社製）等の市販品を用いてもよい。
式（ｄ３）で表される部分構造を有する化合物としては、例えば、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、２−ヒドロキシ−２−メチル−１−〔４−（２−ヒドロキシエトキシ）フェニル〕プロパン−１−オン、１−ヒドロキシシクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチル−１−（４−イソプロペニルフェニル）プロパン−１−オンのオリゴマー、α，α−ジエトキシアセトフェノン、ベンジルジメチルケタール等が挙げられる。
感度の点で、前記アルキルフェノン化合物としては、式（ｄ２）で表される部分構造を有する化合物が好ましく、２−メチル−２−モルホリノ−１−（４−メチルスルファニルフェニル）プロパン−１−オン及び２−ジメチルアミノ−１−（４−モルホリノフェニル）−２−ベンジルブタン−１−オンがより好ましい。 The alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In these partial structures, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4 -Morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one Etc. Commercial products such as Irgacure (registered trademark) 369, 907 and 379 (manufactured by BASF) may be used.
Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2 -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxy Examples include acetophenone and benzyl dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2), such as 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one. And 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one is more preferred.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl). ) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2- Methylphenyl) ete Le] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercial products such as Irgacure (registered trademark) 819 (manufactured by Ciba Japan) may be used.

前記オキシム化合物としては、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）ブタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）−３−シクロペンチルプロパン−１−オン−２−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−｛２−メチル−４−（３，３−ジメチル−２，４−ジオキサシクロペンタニルメチルオキシ）ベンゾイル｝−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−イミン、Ｎ−ベンゾイルオキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−オン−２−イミン等が挙げられる。イルガキュア（登録商標）ＯＸＥ０１、ＯＸＥ０２（以上、ＢＡＳＦジャパン社製）、Ｎ−１９１９（ＡＤＥＫＡ社製）等の市販品を用いてもよい。 The oxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond.

Examples of the oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclo) Pentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- 2-Methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 -Yl] -3-cyclopentylpropane-1-one-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF Japan), N-1919 (manufactured by ADEKA) may be used.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4, 4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2 -Chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxy) Nyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), and the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (for example, see JP-A-7-10913). Preferably, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5 Examples include 5'-tetraphenylbiimidazole and 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole.

  Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant (D1) (particularly amines) described later.

  Examples of the acid generator that generates an acid by light include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4 -Onium salts such as acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, Examples thereof include nitrobenzyl tosylate and benzoin tosylate.

  The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part by mass. If the content of the photopolymerization initiator is within the above range, a colored pattern can be formed with high sensitivity, so that the exposure time tends to be shortened and the productivity tends to be improved.

The colored curable resin composition of the present invention may further contain a polymerization initiation assistant (D1). The polymerization initiation assistant (D1) is usually used in combination with the polymerization initiator (D), and is a compound or sensitizer used for accelerating the polymerization of a polymerizable compound initiated by the polymerization initiator. It is.
Examples of the polymerization initiation assistant (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.
Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 2-dimethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (Ethylmethylamino) benzophenone and the like can be mentioned, among which 4,4′-bis (diethylamino) benzophenone is preferable. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

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

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.
The polymerization initiation assistants may be used alone or in combination of two or more.

  When these polymerization initiation assistants (D1) are used, the amount used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Preferably it is 1-20 mass parts. When the amount of the polymerization initiation assistant (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the colored pattern tends to be improved.

The colored curable resin composition of the present invention preferably contains a solvent (E).
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (intramolecular) Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O-,- Solvents not containing CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like can be used.

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

  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, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, like methyl anisole.

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and the like diethylene glycol monobutyl ether acetate.

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

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

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

Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
These solvents may be used alone or in combination of two or more.

  Among the above-mentioned solvents, an organic solvent having a boiling point at 1 atm of 120 ° C. or higher and 180 ° C. or lower is preferable from the viewpoints of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide and the like are preferable, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate and the like are more preferable.

In particular, a solvent containing propylene glycol monomethyl ether is preferable. Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene Consists only of at least one selected from the group consisting of glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide A solvent is more preferable. When these solvents are used, the flatness at the time of coating is good, and the generation of foreign matters is small when a color filter is formed.
When the solvent (E) is a solvent containing propylene glycol monomethyl ether, the content of propylene glycol monomethyl ether in the solvent (E) is preferably 30% by mass to 80% by mass, and more preferably 50% by mass to 70% by mass. The following is more preferable.

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

The colored curable resin composition of the present invention may further contain a surfactant (G). Examples of the surfactant (G) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone surfactant include a surfactant having a siloxane bond. Specifically, Torre Silicone (trade name) DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH30PA, SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (made by Momentive Performance Materials Japan GK) Is mentioned.

  Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.), E5844 (Daikin Fine Chemical Laboratory Co., Ltd.) and the like.

Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation) and the like can be mentioned.
These surfactants may be used alone or in combination of two or more.

  The content of the surfactant (G) is preferably 0.001% by mass or more and 0.2% by mass or less, and preferably 0.002% by mass with respect to the total amount of the colored curable resin composition of the present invention. The content is 0.1% by mass or less, more preferably 0.01% by mass or more and 0.05% by mass or less. When the content of the surfactant (G) is in the above range, the flatness of the color filter can be improved.

  The colored curable resin composition of the present invention is known in the technical field as necessary, fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents. Various additives (hereinafter sometimes referred to as “other components”).

The colored curable resin composition of the present invention includes, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a polymerization initiation auxiliary agent used as necessary ( It can be prepared by mixing D1), solvent (E), surfactant (F) and other components.
It is preferable to prepare a solution by dissolving compound (1) in part or all of the solvent (E) in advance. The solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.
When the pigment is contained, it is preferable to mix the pigment with a part or all of the solvent (E) in advance and to disperse the pigment using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. The desired colored curable resin composition can be prepared by mixing the remaining components and the like in the obtained pigment dispersion so as to have a predetermined concentration.
The colored curable resin composition prepared by mixing as described above is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.

Examples of the method for forming the color pattern of the color filter with the colored photosensitive resin composition of the present invention include a photolithographic method and a method using an inkjet device. Photolithographic methods include, for example, applying the colored photosensitive resin composition of the present invention onto a substrate, removing a volatile component such as a solvent and drying to form a colored composition layer, and passing through a photomask. In this method, the colored composition layer is exposed and developed. After development, a colored pattern can be formed by heating as necessary. In the above photolithographic method, a colored coating film that is a cured product of the colored composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and the colored coating film thus obtained are the color filter of the present invention.
The film thickness of the color filter to be produced is not particularly limited, and can be appropriately adjusted depending on the material used, the use, and the like.

  According to the colored curable resin composition of the present invention, a color filter having particularly excellent brightness can be produced. Therefore, the color filter is useful as a color filter used for a display device (for example, a liquid crystal display device, an organic EL device, electronic paper) or a solid-state image sensor.

  Next, the present invention will be described more specifically with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

[Synthesis Example 1]
After adding 250 parts of water and 50 parts of N-methylpyrrolidone to 25.0 parts of o-toluidine-4-sulfonic acid tetrahydrate represented by the formula (a-1), 30% water is added under ice cooling. The pH was adjusted to 7-8 with an aqueous sodium oxide solution. The following operations were performed under ice cooling. 18.4 parts of sodium nitrite was added and stirred for 30 minutes. After adding 64.8 parts of 35% hydrochloric acid little by little to make a brown solution, the mixture was stirred for 2 hours. An aqueous solution obtained by dissolving 16.7 parts of amidosulfuric acid in 170 parts of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.

  After adding 173 parts of water and 19 parts of N-methylpyrrolidone to 19.3 parts of 1-butyl-3-cyano-4-methyl-6-hydroxypyrid-2-one represented by the formula (c-1) Under ice cooling, the pH was adjusted to 8-9 with a 30% aqueous sodium hydroxide solution.

  The following operations were performed under ice cooling. The pyridone aqueous solution was stirred to obtain a colorless solution, and then the suspension containing the diazonium salt was added dropwise by a pump over 2 hours while adjusting the pH to 8 to 9 with a 30% aqueous sodium hydroxide solution. After completion of dropping, the solution was further stirred for 2 hours to obtain a dark solution. 140 parts of purified salt was added to the reaction solution and stirred for 5 hours. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 35.8 parts (yield 91%) of the compound represented by the formula (d-1).

Compound (d-1) 0.35 g was dissolved in N, N-dimethylformamide to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with water to a volume of 100 cm ³ (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, cell length is 1 cm). This compound showed an absorbance of 3.1 (arbitrary unit) at λmax = 441 nm.

  Into a flask equipped with a condenser and a stirrer, 5.0 parts of compound (d-1), 25 parts of acetonitrile and 1.8 parts of N, N-dimethylformamide were charged, while maintaining at 20 ° C. or lower with stirring. 2.8 parts of thionyl chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 40 ° C., the reaction was continued for 2 hours at the same temperature, and then cooled to 20 ° C. The cooled reaction solution was poured into 150 parts of ice water with stirring and then stirred for 30 minutes. The precipitated yellow crystals were separated by filtration, washed well with tap water, and dried at 2 room temperature for 1 hour. Prepare a flask equipped with a condenser and a stirrer separately, add 1.9 parts of 3-amino-1-propanol and 20 parts of N-methylpyrrolidone, and adjust first while maintaining at 20 ° C. or lower with stirring. The yellow crystals obtained were added over 1 hour. After adding the yellow solid, the liquid temperature was raised to room temperature, and then the reaction solution was stirred for 30 minutes. After adding 40 parts of methanol to the reaction solution and stirring, this mixed solution was added to a mixed solution of 29 parts of acetic acid and 300 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion exchange water, and dried under reduced pressure at 60 ° C. to obtain 4.2 parts (yield 73%) of the compound represented by the formula (III-1).

Compound (III-1) 0.35 g was dissolved in ethyl lactate to a volume of 250 cm ³ , of which 2 cm ³ was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L). The absorption spectrum was measured using a photometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.8 (arbitrary unit) at λmax = 435 nm.

The following reaction was performed in a nitrogen atmosphere. After adding 8.0 parts of N-methylpyrrolidone to 4.0 parts of compound (III-1), the reaction solution was prepared by stirring for 30 minutes. While stirring the reaction solution at room temperature, 1.1 parts of succinic acid chloride was added dropwise. After completion of dropping, the mixture was further stirred for 8 hours. After pouring the reaction solution into 500 parts of water, 240 parts of ethyl acetate was added and stirred for 30 minutes. After separating the organic phase using a separatory funnel, it was further washed with 1000 parts of water, 1000 parts of a 10% aqueous sodium carbonate solution, 1000 parts of a 10% aqueous acetic acid solution, and 1000 parts of ion-exchanged water. The separated organic phase was distilled off to obtain 4.0 parts of a compound represented by the formula (I-2) (hereinafter sometimes referred to as “compound (I-2)”). Yield 92%.

The structure of compound (I-2) was determined by mass spectrometry. As the mass spectrometer, JMS-700 (manufactured by JEOL Ltd.) was used.
Mass spectrometry: ionization mode = FD +: m / z = 1004

Compound (I-2) 0.35 g was dissolved in ethyl lactate to a volume of 250 cm ³ , of which 2 cm ³ was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L). The absorption spectrum was measured using a photometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.5 (arbitrary unit) at λmax = 435 nm.

[Synthesis Example 2]
After adding 200 parts of water and 50 parts of N-methylpyrrolidone to 25.0 parts of m-toluidine-4-sulfonic acid represented by the formula (a-2), the pH is 7 with 30% aqueous sodium hydroxide solution under ice cooling. Adjusted to ~ 8. The following operations were performed under ice cooling. 27.6 parts of sodium nitrite was added and stirred for 30 minutes. After adding 97.3 parts of 35% hydrochloric acid little by little to give a brown solution, the mixture was stirred for 2 hours. An aqueous solution obtained by dissolving 25.1 parts of amidosulfuric acid in 250 parts of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.

  To 28.9 parts of 1-butyl-3-cyano-4-methyl-6-hydroxypyrid-2-one represented by the formula (c-1), 260 parts of water and 28.9 parts of N-methylpyrrolidone were added. After that, the pH was adjusted to 8-9 with 30% aqueous sodium hydroxide solution under ice cooling.

  The following operations were performed under ice cooling. The pyridone aqueous solution was stirred to obtain a colorless solution, and then the suspension containing the diazonium salt was added dropwise by a pump over 2 hours while adjusting the pH to 8 to 9 with a 30% aqueous sodium hydroxide solution. After completion of dropping, the solution was further stirred for 2 hours to obtain a dark solution. 140 parts of purified salt was added to the reaction solution and stirred for 5 hours. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 46.7 parts (yield 79%) of the compound represented by the formula (d-2).

Compound (d-2) 0.35 g was dissolved in N, N-dimethylformamide to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with water to a volume of 100 cm ³ (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, cell length is 1 cm). This compound exhibited an absorbance of 3.2 (arbitrary unit) at λmax = 435 nm.

  Into a flask equipped with a condenser and a stirrer, 5.0 parts of compound (d-2), 25 parts of acetonitrile and 1.8 parts of N, N-dimethylformamide are added, and the temperature is maintained at 20 ° C. or lower with stirring. 2.8 parts of thionyl chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 40 ° C., the reaction was continued for 2 hours at the same temperature, and then cooled to 20 ° C. The cooled reaction solution was poured into 150 parts of ice water with stirring and then stirred for 30 minutes. The precipitated yellow crystals were separated by filtration, washed well with tap water, and dried at 2 room temperature for 1 hour. Prepare a flask equipped with a condenser and a stirrer separately, add 1.9 parts of 1-amino-2-propanol and 20 parts of N-methylpyrrolidone, and adjust in advance while maintaining at 20 ° C. or lower with stirring. The yellow crystals obtained were added over 1 hour. After adding the yellow solid, the liquid temperature was raised to room temperature, and then the reaction solution was stirred for 30 minutes. After adding 40 parts of methanol to the reaction solution and stirring, this mixed solution was added to a mixed solution of 29 parts of acetic acid and 300 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion exchange water, and dried under reduced pressure at 60 ° C. to obtain 4.4 parts (yield 77%) of the compound represented by the formula (III-2).

Compound (III-2) 0.35 g was dissolved in ethyl lactate to a volume of 250 cm ³ , of which 2 cm ³ was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L). The absorption spectrum was measured using a photometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.7 (arbitrary unit) at λmax = 432 nm.

The following reaction was performed in a nitrogen atmosphere. After adding 50.0 parts of N-methylpyrrolidone to 25.0 parts of compound (III-2), the reaction solution was prepared by stirring for 30 minutes. While stirring the reaction solution at room temperature, 5.0 parts of adipic acid chloride was added dropwise. After completion of dropping, the mixture was further stirred for 8 hours. After pouring the reaction solution into 1000 parts of water, 500 parts of ethyl acetate was added and stirred for 30 minutes. After separating the organic phase using a separatory funnel, it was further washed with 2000 parts of water, 2000 parts of 10% aqueous sodium carbonate solution, 2000 parts of 10% aqueous acetic acid solution, and 2000 parts of ion-exchanged water. The separated organic phase was evaporated to obtain 24.7 parts of a compound represented by the formula (I-5) (hereinafter sometimes referred to as “compound (I-5)”). Yield 88%.

The structure of compound (I-5) was determined by mass spectrometry. As the mass spectrometer, JMS-700 (manufactured by JEOL Ltd.) was used.
Mass spectrometry: ionization mode = FD +: m / z = 1032

Compound (I-5) 0.35 g was dissolved in ethyl lactate to a volume of 250 cm ³ , of which 2 cm ³ was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L). The absorption spectrum was measured using a photometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.3 (arbitrary unit) at λmax = 431 nm.

[Synthesis Example 3]
200 parts of water was added to 10 parts of m-toluidine-4-sulfonic acid (compound represented by formula (a-2)), and then adjusted to pH 7-8 with 30% aqueous sodium hydroxide solution under ice cooling. The following operations were performed under ice cooling. 11.1 parts of sodium nitrite was added and stirred for 30 minutes. After adding 39 parts of 35% hydrochloric acid little by little to give a brown solution, the mixture was stirred for 2 hours. An aqueous solution obtained by dissolving 10.1 parts of amidosulfuric acid in 101 parts of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.

  14 parts of 1- (2-ethylhexyl) -3-cyano-4-methyl-6-hydroxypyrid-2-one (a compound represented by the formula (c-2)), 125 parts of water and 25 parts of N-methylpyrrolidone After adding a portion, the mixture was adjusted to pH 8-9 with 30% aqueous sodium hydroxide solution under ice cooling.

  The following operations were performed under ice cooling. The pyridone aqueous solution was stirred to obtain a colorless solution, and then the suspension containing the diazonium salt was added dropwise by a pump over 2 hours while adjusting the pH to 8 to 9 with a 30% aqueous sodium hydroxide solution. After completion of dropping, the mixture was further stirred for 2 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 21.4 parts (yield 87%) of the compound represented by the formula (d-3).

Compound (d-3) 0.35 g was dissolved in N, N-dimethylformamide to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with water to a volume of 100 cm ³ (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.9 (arbitrary unit) at λmax = 433 nm.

  Into a flask equipped with a condenser and a stirrer, 5.0 parts of compound (d-3), 35 parts of acetonitrile and 1.6 parts of N, N-dimethylformamide were added, while maintaining at 20 ° C. or lower with stirring. 2.4 parts of thionyl chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 40 ° C., the reaction was continued for 2 hours at the same temperature, and then cooled to 20 ° C. The cooled reaction solution was poured into 150 parts of ice water with stirring and then stirred for 30 minutes. The precipitated yellow crystals were separated by filtration, washed well with tap water, and dried under reduced pressure at 60 ° C. for 2 hours. Prepare a flask equipped with a condenser and a stirrer separately, add 2.0 parts of 1-amino-2-propanol and 20 parts of N-methylpyrrolidone, and adjust in advance while maintaining the temperature at 20 ° C. or lower with stirring. The yellow crystals obtained were added over 1 hour. After adding the yellow crystals, the liquid temperature was raised to room temperature, and then the reaction solution was stirred for 30 minutes. After adding 40 parts of methanol to the reaction solution and stirring, this mixed solution was added to a mixed solution of 29 parts of acetic acid and 300 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion exchange water, and dried under reduced pressure at 60 ° C. to obtain 3.9 parts (yield 69%) of the compound represented by the formula (III-3).

Compound (III-3) 0.35 g was dissolved in ethyl lactate to a volume of 250 cm ³ , of which 2 cm ³ was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L). The absorption spectrum was measured using a photometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.3 (arbitrary unit) at λmax = 431 nm.

  The following reaction was performed in a nitrogen atmosphere. 150 parts of N-methylpyrrolidone was added to 49.9 parts of compound (III-3), and then stirred for 30 minutes to prepare a reaction solution. While stirring the reaction solution at room temperature, 6.8 parts of sebacic acid chloride was added dropwise. After completion of dropping, the mixture was further stirred for 8 hours. 7.8 parts of adipic acid chloride was added dropwise. After completion of dropping, the mixture was further stirred for 8 hours. After pouring the reaction solution into 300 parts of water, 80 parts of ethyl acetate was added and stirred for 30 minutes. The organic phase was separated using a separatory funnel, and further washed with 500 parts of water, 3000 parts of a 10% aqueous sodium carbonate solution, 1000 parts of an aqueous 10% acetic acid solution, and 1000 parts of ion-exchanged water. The separated organic phase was evaporated to obtain 2.0 parts of dye (I), which is a mixture of the compound represented by formula (I-6) and the compound represented by formula (I-7). It was. Yield 85%.

Dissolve 0.35 g of dye (I) in ethyl lactate to a volume of 250 cm ³ , of which 2 cm ³ is diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L), spectrophotometer The absorption spectrum was measured using (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.2 (arbitrary unit) at λmax = 431 nm.

<Measurement of content ratio in mixture>
The content ratio of the compound represented by the formula (I-6) and the compound represented by the formula (I-7) in the dye (I) is measured by a calibration curve method using liquid crystal chromatography (HPLC). did. The calibration curve method is a method for determining an unknown concentration from the concentration-absorbance relationship of a standard solution row of a known concentration when determining the concentration of a substance in a solution.

HPLC system Prominence (manufactured by Shimadzu Corporation)
Liquid feeding unit: Two LC-20AT
Autosampler: One SIL-20A
Column oven: One CTO-20A
UV detector: One SPD-20A
Online degasser: DGU-20A single column Wakosil II 3C18HG (3μm, 3mmφ × 150mm)
Mobile phase A solution: 0.1% TBAB / water: acetonitrile (9: 1)
Liquid B: 0.1% TBAB / water: acetonitrile (1: 9)
Gradient (liquid B)
B initial concentration 25%
25% → (30 minutes) → 100% (20 minutes hold)
Detection wavelength 254nm
Column temperature 40 ° C
Flow rate 0.5mL / min
Injection volume 5μL
TBAB: Tetrabutylammonium bromide

  The compound represented by the formula (I-6) and the compound represented by the formula (I-7) were each dissolved in acetonitrile to prepare a solution having a concentration described in Table 22. The solution was subjected to liquid crystal chromatography analysis under the above conditions, and the elution time and peak area were measured. The results are shown in Table 22.

From the concentration of the solution and the measured peak area, a calibration curve was obtained as the following equation.
Calibration curve of the compound represented by the formula (I-6): (peak area) = 72.2 × (concentration)
Calibration curve of compound represented by formula (I-7): (peak area) = 76.0 × (concentration)

Dye (I) 13.9 mg was dissolved in acetonitrile to a volume of 50 cm ³ (concentration: 0.278 g / L), liquid crystal chromatography analysis was performed under the above conditions, and elution time and peak area were measured. The compound represented by formula (I-7) was eluted at an elution time of 35.9 minutes, and the peak area was 944436. The compound represented by the formula (I-6) was eluted at an elution time of 37.9 minutes, and the peak area was 1108707.
Using the above calibration curve, the content ratio of each compound in the mixture (A) was determined. As a result, the compound represented by the formula (I-6) / the compound represented by the formula (I-7) = 44 7 / 55.3.

[Synthesis Example 4]
A four-necked flask was charged with 106.4 parts of tetrachlorophthalonitrile, 14.3 parts of zinc chloride, 84.0 parts of urea, 19.9 parts of ammonium molybdate tetrahydrate, and 100 parts of methylnaphthalene, and a nitrogen atmosphere Under heating at 200 ° C. for 6 hours. The precipitate was collected by filtration, washed with methanol and then with hot water at 60 ° C., and then dried under reduced pressure at 60 ° C. to obtain 29.7 parts of hexadecachlorozinc phthalocyanine.
Next, 90.7 parts of anhydrous aluminum chloride and 11.7 parts of sodium chloride were mixed at 40 ° C. in a four-necked flask, and 25.0 parts of hexadecachlorozinc phthalocyanine was added and stirred. 60.0 parts were added dropwise, and the temperature was raised to 130 ° C. over 20 hours and held for 1 hour. The obtained reaction product was taken out into water, and a chlorinated brominated zinc phthalocyanine crude pigment was precipitated. This crude chlorinated brominated phthalocyanine pigment slurry was filtered, washed with warm water at 60 ° C., then washed with 1% aqueous sodium hydrogen sulfate solution, further washed with warm water at 60 ° C., and dried under reduced pressure at 60 ° C. .3 parts of purified chlorinated brominated zinc phthalocyanine crude pigment were obtained.
Next, 20 parts of the crude chlorinated brominated zinc phthalocyanine pigment obtained in the above operation, 60 parts of sodium chloride and 20 parts of diethylene glycol were charged into a kneader, ground at 90 ° C. for 5 hours, and then taken out into 100 parts of an 80 ° C. aqueous solution. After stirring for 30 minutes, it is filtered, washed with warm water at 60 ° C., dried under reduced pressure at 60 ° C., and pulverized to be 12.8 parts of chlorinated brominated zinc phthalocyanine pigment 1 (hereinafter sometimes referred to as “zinc phthalocyanine pigment 1”). )
As a result of analyzing the obtained zinc phthalocyanine pigment 1 by flask combustion treatment ion chromatography, the ratio of substituents on the zinc phthalocyanine skeleton was bromine 14.6, chlorine 1.4, and hydrogen 0.

[Synthesis Example 5]
In a four-necked flask, 89.1 parts of sulfuryl chloride, 90.7 parts of anhydrous aluminum chloride and 12.3 parts of sodium chloride were mixed at 40 ° C., and 25.0 parts of zinc phthalocyanine was added and stirred. 60.0 parts of bromine was added dropwise, the temperature was raised to 130 ° C. over 20 hours, and held for 1 hour. The obtained reaction product was taken out into water, and a chlorinated brominated zinc phthalocyanine crude pigment was precipitated. This chlorinated brominated zinc phthalocyanine crude pigment slurry was filtered, then washed with warm water at 60 ° C., then washed with 1% aqueous sodium hydrogen sulfate solution, further washed with warm water at 60 ° C., and dried under reduced pressure at 60 ° C., 22.5 parts of purified chlorinated brominated zinc phthalocyanine crude pigment were obtained.
Next, 20 parts of the crude chlorinated brominated zinc phthalocyanine pigment obtained in the above operation, 60 parts of sodium chloride and 20 parts of diethylene glycol were charged into a kneader, ground at 90 ° C. for 5 hours, and then taken out into 100 parts of an 80 ° C. aqueous solution. After stirring for 30 minutes, filtration, washing with warm water at 60 ° C., drying under reduced pressure at 60 ° C., and pulverization, there are cases where 14.3 parts of chlorinated brominated zinc phthalocyanine pigment 2 (hereinafter referred to as “zinc phthalocyanine pigment 2”). )
As a result of analyzing the obtained zinc phthalocyanine pigment 2 by flask combustion treatment ion chromatography, the ratio of substituents on the zinc phthalocyanine skeleton was bromine 13.4, chlorine 2.2, and hydrogen 0.4.

一方、重合開始剤２，２’−アゾビス（２，４−ジメチルバレロニトリル）３０質量部を３−メトキシブチルアセテート２２５質量部に溶解した溶液を、別の滴下ロートを用いて４時間かけてフラスコ内に滴下した。重合開始剤の溶液の滴下が終了した後、４時間、７０℃に保持し、その後室温まで冷却して、重量平均分子量Ｍｗは、１．３×１０^４、分子量分布は２．５、固形分３３質量％、溶液酸価３４ｍｇ−ＫＯＨ／ｇの樹脂Ｂ１溶液を得た。上記の固形分と溶液酸価とから計算して、樹脂Ｂ１の固形分酸価は１００ｍｇ−ＫＯＨ／ｇである。樹脂Ｂ１は下記に示す構造単位を有する。 [Synthesis Example 6]
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, and 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added. Heat to 70 ° C. with stirring. Next, 60 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the following formula (B1-1) and a formula (B2-1)) The compound represented is mixed at a molar ratio of 50:50.) A solution is prepared by dissolving in 240 parts by mass and 140 parts by mass of 3-methoxybutyl acetate. Over time, it was dripped in the flask kept at 70 degreeC.

On the other hand, a solution obtained by dissolving 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of 3-methoxybutyl acetate was added to a flask over another 4 hours using another dropping funnel. It was dripped in. After completion of the dropwise addition of the polymerization initiator solution, the temperature was kept at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight Mw was 1.3 × 10 ⁴ , the molecular weight distribution was 2.5, and the solid content. A resin B1 solution having 33% by mass and a solution acid value of 34 mg-KOH / g was obtained. Calculated from the solid content and the solution acid value, the solid content acid value of the resin B1 is 100 mg-KOH / g. Resin B1 has the structural units shown below.

[Synthesis Example 7]
Into a 1000 ml flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a gas introduction tube, 333 g of propylene glycol monomethyl ether acetate was placed. Thereafter, nitrogen gas was introduced into the flask using a gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. Then, after raising the temperature of the solvent in the flask to 100 ° C., 22.0 g (0.10 mol) of dicyclopentanyl methacrylate (FA-513M; manufactured by Hitachi Chemical Co., Ltd.), 70.5 g of benzyl methacrylate (0 .40 mol), 43.0 g (0.5 mol) of methacrylic acid, 3.6 g of azobisisobutyronitrile and 164 g of propylene glycol monomethyl ether acetate were added dropwise to the flask using a dropping funnel over 2 hours. After completion of the dropwise addition, stirring was further continued at 100 ° C. for 5 hours.
After completion of the stirring, air was introduced into the flask using a gas introduction tube, and the atmosphere in the flask was changed to air, and then 35.5 g of glycidyl methacrylate [0.25 mol (mole fraction relative to methacrylic acid used in this reaction). 50 mol%)), 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. for 6 hours to obtain a resin B2 solution having a solid content of 38.7% by mass. Got. Resin B2 had a weight average molecular weight of 9.8 × 10 ³ and a solid content acid value of 82 mgKOH / g.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example were measured using the GPC method under the following conditions.
Apparatus; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector; RI
Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The polystyrene-converted weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was defined as molecular weight distribution.

[Example 1]
<Preparation of zinc phthalocyanine pigment dispersion 1>
Colorant (A); 85 parts of zinc phthalocyanine pigment 1 obtained in Synthesis Example 4 resin (B); propylene glycol monomethyl ether acetate solution of methacrylic acid / benzyl methacrylate copolymer (solid content: 38.7%, weight) Average molecular weight Mw; 2.3 × 10 ⁴ , solid content acid value 138 mg-KOH / g) 66 parts (solid content conversion value: 26 parts)
Pigment dispersant 1: Dispersic 2001 (manufactured by Big Chemie) (mixed solution of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and ethylene glycol monobutyl ether having a solid content of 46.0% by mass) 78 parts (in terms of solid content: 36 copies)
Solvent (E): 136 parts of propylene glycol monomethyl ether Solvent (E): 136 parts of propylene glycol monomethyl ether acetate are placed in a 143 ml mayonnaise bottle, and further 166.500 parts by mass of zirconia beads having a diameter of 0.5 mm are added and sealed. Shake for 20 hours in a paint conditioner. Then, the zinc phthalocyanine pigment dispersion 1 was obtained by filtering and removing a zirconia bead.

<Preparation of colored curable resin composition 1>
Next, each component was mixed by the following mixing | blending, and the colored curable resin composition 1 was obtained.
Zinc phthalocyanine pigment dispersion 1 38 parts Colorant (A); Compound (I-2) obtained in Synthesis Example 1 2.1 parts Resin (B); Resin B1 solution obtained in Synthesis Example 6 11 parts Polymerizability Compound (C): Dipentaerythritol hexaacrylate ((KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 4 parts polymerization initiator (D); 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane -1-one (Irgacure 369; manufactured by BASF Japan Ltd.) 1.4 parts polymerization initiation assistant (D1): 4,4′-bis (diethylamino) benzophenone
(EAB-F; manufactured by Hodogaya Chemical Co., Ltd.) 0.5 parts solvent (E); propylene glycol monomethyl ether 40 parts solvent (E); ethyl 3-ethoxypropionate 3.9 parts surfactant (G) ; Mega Fuck F475 (manufactured by DIC Corporation) 0.01 parts

<Preparation of colored pattern>
A colored curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning) by spin coating, and then pre-baked at 100 ° C. for 3 minutes to form a colored composition layer. After cooling, the distance between the substrate on which the colored composition layer is formed and the photomask made of quartz glass is set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) is used in an air atmosphere at 200 mJ / Light irradiation was performed with an exposure amount of cm ² (based on 365 nm). A photomask having a 100 μm line and space pattern was used. The colored composition layer after the light irradiation is developed by immersing in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23 ° C. for 80 seconds, washed with water, After baking at 20 ° C. for 20 minutes, a colored pattern was obtained. After standing to cool, the thickness of the obtained colored pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.) and found to be 2.2 μm.

<Chromaticity evaluation>
About the obtained coloring pattern, spectroscopy was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity coordinate in the XYZ color system of CIE was used using the characteristic function of C light source. (X, y) and tristimulus value Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Table 23.

<Solvent resistance evaluation>
The obtained colored pattern was immersed in N-methylpyrrolidone at 23 ° C. for 30 minutes, and the color xy chromaticity coordinates (x, y) and tristimulus value Y before and after immersion were measured by the above method. The color difference ΔEab * was calculated by the method described in JIS Z 8730: 2009 (7. Color difference calculation method). The smaller the value of ΔEab *, the smaller the color change before and after immersion. The results are shown in Table 23.

[Example 2]
A colored curable resin composition 2 was prepared in the same manner as in Example 1 except that Compound (I-2) was replaced with 2.1 parts of Compound (I-5) obtained in Synthesis Example 2 in Example 1. Obtained. About the coloring curable resin composition 2, the coloring pattern was produced by the method similar to Example 1, and evaluation was performed. The results are shown in Table 23.

Example 3
In Example 1, colored curable resin composition 3 was obtained in the same manner as in Example 1 except that compound (I-2) was replaced with 2.0 parts of dye (I) obtained in Synthesis Example 3. . About the coloring curable resin composition 2, the coloring pattern was produced by the method similar to Example 1, and evaluation was performed. The results are shown in Table 23.

Example 4
<Preparation of zinc phthalocyanine pigment dispersion 2>
Colorant (A): 40 parts of zinc phthalocyanine pigment 2 obtained in Synthesis Example 5 Pigment dispersant 1: Dispersic 2001 (manufactured by BYK Chemie) (propylene glycol monomethyl ether, propylene glycol monomethyl ether having a solid content of 46.0% by mass) A mixed solution of acetate and ethylene glycol monobutyl ether) 78 parts (solid content conversion value: 36 parts)
Solvent (E): 137 parts of propylene glycol monomethyl ether were mixed and the pigment was sufficiently dispersed using a bead mill to obtain a zinc phthalocyanine pigment dispersion 2.

<Preparation of colored curable resin composition 4>
Next, each component was mixed by the following mixing | blending, and the colored curable resin composition 4 was obtained.
Zinc phthalocyanine pigment dispersion 2 38 parts Colorant (A); Dye (A) obtained in Synthesis Example 3 2.0 parts Resin (B); Resin B1 solution obtained in Synthesis Example 6 11 parts Polymerizable compound ( C); dipentaerythritol hexaacrylate ((KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 4 parts polymerization initiator (D); 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1 -ON (Irgacure 369; manufactured by BASF Japan Ltd.) 1.4 parts Polymerization initiation aid (D1): 4,4'-bis (diethylamino) benzophenone
(EAB-F; manufactured by Hodogaya Chemical Co., Ltd.) 0.5 parts solvent (E); propylene glycol monomethyl ether 30 parts solvent (E); propylene glycol monomethyl ether acetate 10 parts solvent (E); 3-ethoxypropion Ethyl acid 3.9 parts Surfactant (G); Megafac F475 (manufactured by DIC Corporation) 0.01 parts

[Comparative Example 1]
In Example 1, 2.1 parts of compound (I-2) were added to C.I. I. A colored curable resin composition 5 was obtained in the same manner as in Example 1 except that 1.5 parts of Solvent Yellow 162 (a compound represented by the following formula) was replaced with 1.5 parts. About the colored curable resin composition 5, the colored pattern was produced by the same method as Example 1, and evaluated. The results are shown in Table 23.

  From the above results, it was confirmed that the colored pattern formed by the colored curable resin composition of the present invention exhibits high brightness. From this, it can be seen that according to the colored curable resin composition of the present invention, it is possible to obtain a color filter with high brightness.

  According to the colored curable resin composition of the present invention, a color filter with high brightness can be formed.

Claims (7)

Including colorants, resins, polymerizable compounds, polymerization initiators and solvents,
A colored curable resin composition, wherein the colorant is a colorant comprising a compound represented by formula (I) and a zinc phthalocyanine compound.

[In Formula (I), Z ¹ , Z ² and L ¹ each independently represent a C 1-16 divalent aliphatic hydrocarbon group which may have a substituent, and the aliphatic —CH ₂ — contained in the hydrocarbon group may be replaced by —CO— or —O—.
R ¹ and R ² are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, or a carbon atom having 2 to 2 carbon atoms which may have a substituent. 18 acyl groups are represented.
A ¹ and A ² each independently represent a C 6-14 divalent aromatic hydrocarbon group which may have a substituent.
B ¹ and B ² are each independently a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a C ^{3 to} 14 carbon group which may have a substituent. A monovalent heterocyclic group is represented, and —CH ₂ — contained in the heterocyclic group may be replaced by —CO—. ] The colored curable resin composition according to claim 1, wherein the zinc phthalocyanine compound is a compound represented by the formula (P).

Wherein ^{(P), A} 1 ^{~A 16} each independently represent a hydrogen atom, a chlorine atom or a bromine atom. ]   The colored curable resin composition according to claim 1 or 2, wherein the colorant is a colorant comprising two or more compounds represented by formula (I) and a zinc phthalocyanine compound.   The colored curable resin composition according to any one of claims 1 to 3, wherein the colorant is a colorant comprising a compound represented by the formula (I) and a zinc phthalocyanine pigment.   The colored curable resin composition according to any one of claims 1 to 4, wherein the solvent is a solvent containing propylene glycol monomethyl ether.   The color filter formed with the colored curable resin composition as described in any one of Claims 1-5.   A display device comprising the color filter according to claim 6.