JP2010009033A - Colored curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored curable composition which enables to manufacture a color filter excellent in solvent resistance. <P>SOLUTION: The colored curable composition comprises a dye (A), a polymerizable compound (B) and a binder resin (C), wherein the binder resin (C) is a copolymer comprising a constitutional unit derived from a compound (C0) having a carbon-carbon unsaturated double bond and a cyclic ether structure, and a constitutional unit derived from at least one compound (C2) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a colored curable composition.

  Colored curable compositions are used for the production of color filters used in display devices such as liquid crystal display panels, electroluminescence panels, and plasma display panels. In this colored curable composition, it is known to use a pigment or a dye as a colorant (Non-patent Document 1).

P112 (Nikkan Kogyo Shimbun Co., Ltd. issued the first 2nd edition on March 31, 2005)

  The objective of this invention is providing the colored curable composition which can form the color filter excellent in solvent resistance.

  As a result of repeated studies to find a colored curable composition that can solve the above-described problems, the present inventors have reached the present invention.

That is, the present invention is the following invention.
1. Containing dye (A), polymerizable compound (B), binder resin (C),
The binder resin (C) is selected from the group consisting of a structural unit derived from the compound (C0) having a carbon-carbon unsaturated double bond and a cyclic ether structure, and an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. A colored curable composition comprising a copolymer containing a structural unit derived from at least one compound (C2).
2. 2. The colored curable composition according to item 1 above, wherein the cyclic ether structure is an aliphatic polycyclic epoxy structure.
3. The compound (C0) having a carbon-carbon unsaturated double bond and a cyclic ether structure is at least selected from the group consisting of a compound represented by the formula (C1-1) and a compound represented by the formula (C1-2). 3. The colored curable composition according to 1 or 2 above, which is a single compound.

[In formula (C1-1) and formula (C1-2), R represents a C1-C4 alkyl group which may be independently substituted with a hydrogen atom or a hydroxyl group.
X represents a C1-C6 alkylene group which may contain a single bond or a hetero atom each independently. ]

4). The colored curable composition according to any one of the preceding items 1 to 3, wherein the dye (A) is a dye containing a dye having a carboxyl group.
5). The colored curable composition as described in any one of 1 to 4 above, wherein the polymerizable compound (B) is a monomer or oligomer having a carboxyl group.
6). The colored curable composition according to any one of 1 to 5 above, further comprising a pigment.
7). The pattern formed with the photolithographic method or the inkjet method using the coloring curable composition in any one of the preceding 1-6.
8). A color filter comprising the pattern described in 7 above.
9. A liquid crystal display device comprising the color filter according to item 8 above.

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

It does not specifically limit as dye (A), A well-known dye can be used, For example, an oil-soluble dye, an acidic dye, the amine salt of an acidic dye, the sulfonamide derivative of an acidic dye, etc. are mentioned.
Examples of the dye include compounds classified as dyes in the color index (published by The Society of Dyers and Colorists) and known dyes described in dyeing notes (color dyeing company). Includes 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. I. Solvent Red 45, 49, 125, 130, C.I. I. Solvent Orange 2, 7, 11, 15, 26, 56, C.I. I. Solvent Blue 35, 37, 59, 67, C.I. I. Solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 etc. are mentioned. In addition, C.I. I. As an acid dye, C.I. 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. 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. 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. I. Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340, C.I. I. Acid Violet 6B, 7, 9, 17, 19, C.I. I. And dyes such as Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109. In addition, C.I. I. C. as a direct dye 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. 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. I. Direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107, C.I. I. Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, C.I. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104, C.I. I. Examples include direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82. Furthermore, C.I. I. As a modern dye, C.I. I. Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65, C.I. 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. 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. 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. 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. I. Modern dyes 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and the like can be mentioned.

  Examples of the dye (A) include amine salts of acidic dyes represented by formulas (i) to (vii) and sulfonamide derivatives of acidic dyes represented by formulas (viii) to (ix). It is done.

D- (SO ₃ ⁻ ) _m (C _n H _{2n + 1} N ⁺ H ₃ ) _m (i)
D- (SO ₃ ⁻ ) _m {(C _n H _{2n + 1} ) ₂ N ⁺ H ₂ } _m (ii)
D− (SO ₃ ⁻ ) _m {(C _n H _{2n + 1} ) ₃ N ⁺ H} _m (iii)
D- (SO ₃ ⁻ ) _m {(C _n H _{2n + 1} ) ₄ N ⁺ } _m (iv)
D- (SO ₃ ⁻ ) _m (C _e H _{2e + 1} OC _f H _2f N ⁺ H ₃ ) _m (v)
D- (SO ₃ ⁻ ) _m {(C _n H _{2n + 1} ) (PhCH ₂ ) ₂ N ⁺ H} _m (vi)
D- (SO ₃ ⁻ ) _m {(C _n H _{2n + 1} ) Py ⁺ } _m (vii)
_{D - [{SO 2 NH (} C n H 2n + 1)} p] [(SO 3 L) q] (viii)
_{D - [{SO 2 NH (} C e H 2e + 1 OC f H 2f)} p] [(SO 3 L) q] (ix)

（式（Ｉ）中、Ｒ^ａはメチル基を表す。ｍ^ａは、０又は１の整数を表す。）
ｐは、１以上８以下の整数を表す。
ｑは、０以上８以下の整数を表す。
Ｌは、水素原子又は一価の陽イオンを表す。］ [In formulas (i) to (ix), D represents a group derived from a pigment.
m represents an integer of 1 or more and 20 or less.
n represents an integer of 1 or more and 20 or less.
e and f each independently represents an integer of 1 or more and 10 or less.
Ph represents a phenyl group.
Py represents a group represented by the formula (I) connected to C _n H _{2n + 1} by a nitrogen atom.

(In formula (I), R ^a represents ^a methyl group. M ^a represents an integer of 0 or 1.)
p represents an integer of 1 to 8.
q represents an integer of 0 or more and 8 or less.
L represents a hydrogen atom or a monovalent cation. ]

ｐは、好ましくは１以上６以下の整数、より好ましくは１以上５以下の整数を表す。
ｑは、好ましくは０以上６以下の整数、より好ましくは０以上５以下の整数を表す。
Ｌにおける一価の陽イオンとしては、例えば、リチウムイオン、ナトリウムイオン、カリウムイオン、（Ｃ_２Ｈ_５）_３ＨＮ^＋などの４級アンモニウムイオンなどが挙げられ、好ましくはナトリウムイオンが挙げられる。 Specific examples of D include groups derived from azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, and phthalocyanine dyes.
m preferably represents an integer of 1 to 10, more preferably an integer of 1 to 8.
n is preferably an integer of 1 to 10, more preferably an integer of 1 to 8.
e and f each independently preferably represent an integer of 1 to 8, more preferably an integer of 1 to 6.
Py preferably represents a group represented by formula (I-1).

p preferably represents an integer of 1 to 6, more preferably an integer of 1 to 5.
q preferably represents an integer of 0 to 6, more preferably an integer of 0 to 5.
Examples of the monovalent cation in L include lithium ions, sodium ions, potassium ions, quaternary ammonium ions such as (C ₂ H ₅ ) ₃ HN ⁺ , and preferably sodium ions.

  Examples of the azo dye include dyes represented by formulas (1) to (4).

[In formula (1), R ¹ is an alkyl group having 2 to 20 carbon atoms, a cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain, an alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain, and a carbon number. An alkyl group having 2 to 12 carbon atoms substituted with 2 to 12 alkoxyl groups, an alkylcarboxylalkyl group represented by formula (1-1), an alkyloxycarbonylalkyl group represented by formula (1-2), The phenyl group substituted by the C1-C20 alkyl group or the C1-C20 alkyl group substituted by the phenyl group is represented.

L ¹ —CO—OL ² — (1-1)
L ³ —O—CO—L ⁴ — (1-2)

(In formula (1-1), L ¹ represents an alkyl group having 2 to 12 carbon atoms.
L ² represents an alkylene group having 2 to 12 carbon atoms.
Wherein (1-2), ^{L 3} represents an alkyl group having 2 to 12 carbon atoms.
L ⁴ represents an alkylene group having 2 to 12 carbon atoms. )
R ^{2 to} R ⁵ represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, or a halogen atom. ]

Examples of the alkyl group having 2 to 20 carbon atoms include ethyl group, n-propyl group, isopropyl group, n-hexyl group, n-nonyl group, n-decyl group, n-dodecyl group, 2-ethylhexyl group, 1,3 -A dimethylbutyl group, 1-methylbutyl group, 1,5-dimethylhexyl group, 1,1,3,3-tetramethylbutyl group, etc. are mentioned.
Examples of the cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain include a cyclohexylethyl group, a 3-cyclohexylpropyl group, and an 8-cyclohexyloctyl group.
Examples of the alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain include 2-ethylcyclohexyl group, 2-propylcyclohexyl group, and 2- (n-butyl) cyclohexyl group.
Examples of the alkyl group having 2 to 12 carbon atoms substituted by an alkoxyl group having 2 to 12 carbon atoms include 3-ethoxy-n-propyl group, propoxypropyl group, 4-propoxy-n-butyl group, and 3-methyl-n. -Hexyloxyethyl group, 3- (2-ethylhexyloxy) propyl group and the like can be mentioned.
Examples of the phenyl group substituted with an alkyl group having 1 to 20 carbon atoms include an o-isopropylphenyl group.
Examples of the alkyl group having 1 to 20 carbon atoms substituted with a phenyl group include a DL-1-phenylethyl group, a benzyl group, and a 3-phenyl-n-butyl group.
Examples of the alkyl group having 2 to 12 carbon atoms in L1 and L3 include an ethyl group, a propyl group, an n-hexyl group, an n-nonyl group, an n-decyl group, an n-dodecyl group, a 2-ethylhexyl group, 1,3- Examples thereof include a dimethylbutyl group, a 1-methylbutyl group, a 1,5-dimethylhexyl group, and a 1,1,3,3-tetramethylbutyl group.
Examples of the alkylene group having 2 to 12 carbon atoms in L2 and L4 include a dimethylene group and a hexamethylene group.

R ^{2 to} R ⁵ represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group, or a halogen atom. R ^{2 to} R ⁵ include a hydrogen atom, methyl group, ethyl group, n-propyl group, n-butyl group, isopropyl group, sec-butyl group, tert-butyl group, carboxyl group, fluorine atom, chlorine atom, bromine An atom, an iodine atom, etc. are mentioned, Preferably a hydrogen atom, a methyl group, an ethyl group, n-propyl group, n-butyl group, isopropyl group, sec-butyl group, tert-butyl group, a fluorine atom, or a chlorine atom is mentioned. It is done.

Moreover, as a preferable dye among the dyes represented by the formula (1), specifically, a compound represented by the formula (5) may be mentioned.
Examples of the dye having a group derived from an anthraquinone dye include a compound represented by the formula (6).
Examples of the dye having a group derived from a triphenylmethane dye include a compound represented by the formula (7).
Moreover, as a dye which has group derived from a xanthene dye, the compound represented by Formula (8) is mentioned, for example. Examples of the dye having a group derived from a phthalocyanine dye include a compound represented by the formula (9).

The dye (A) is preferably a dye containing a carboxyl group-containing dye because it tends to react with the cyclic ether structure to improve the solvent resistance.
It does not specifically limit as a dye containing a carboxyl group, A well-known substance can be used, For example, the dye etc. which are represented by Formula (10)-Formula (20) are mentioned.

  These dyes are appropriately selected in accordance with the solubility in a solvent and the light fading resistance and spectral spectrum when a color filter pattern is formed using a colored curable composition containing the dye.

  Content of dye (A) is a mass fraction with respect to solid content of a colored curable composition, Preferably it is 5-65 mass%, More preferably, it is 8-60 mass%, Most preferably, it is 10-55 mass%. It is.

  Moreover, when it contains the dye which has a carboxyl group in dye (A), the content is a mass fraction with respect to dye (A), Preferably it is 1-100 mass%, More preferably, it is 5-100 mass. %, Particularly preferably 10 to 100% by mass.

  Here, the solid content in the present specification refers to the total amount of components excluding the solvent contained in the colored curable composition.

  The colored curable composition of the present invention preferably contains a pigment in addition to the dye (A).

Specific examples of the pigment include compounds classified as pigments by Color Index (published by The Society of Dyers and Colorists). Specifically, for example, 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;
C. 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, 36, 58;
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.

  Among them, C.I. I. Pigment yellow 138, 139, 150, C.I. I. Pigment red 177, 209, 242, 254, C.I. I. Pigment red violet 23, C.I. I. Pigment blue 15: 3, 15: 6 and C.I. I. Pigment Green 7, 36, and 58 are preferable.

  When the colored curable composition contains a dye (A) and a pigment, the content of the pigment is a mass fraction with respect to the total amount of the dye (A) and the pigment in the colored curable composition, preferably 2 to 2. It is 98 mass%, More preferably, it is 5-95 mass%, Most preferably, it is 10-95 mass%.

  If necessary, the pigment can be used as a pigment dispersion in a state where the pigment is uniformly dispersed in the solution by performing a dispersion treatment in the presence of a dispersant.

  Examples of the dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine, and may be used alone or in combination of two or more.

  Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines, etc. In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), MegaFuck (manufactured by Dainippon Ink Chemical Co., Ltd.) , FLORARD (manufactured by Sumitomo 3M), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by GENECA), EFKA (manufactured by EFKA CHEMICALS) and PB821 (manufactured by Ajinomoto Co., Inc.) Etc.

  When using a dispersing agent, the usage-amount is a mass fraction with respect to 100 mass% of pigments, Preferably it is 0.1-100 mass%, More preferably, it is 5-50 mass%. It is preferable that the amount of the dispersant used be in the above range because a uniform dispersion tends to be obtained.

  As the polymerizable compound (B), a monomer or an oligomer that is cured by heat or light, or both can be used, and these may be used in combination. A known substance can be used as the monomer or oligomer.

  Specific examples of monomers include pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate derivatives having a carboxyl group, ethylene Oxidized glycerin tri (meth) acrylate, ethylene oxideated trimethylolpropane tri (meth) acrylate, propylene oxided glycerin tri (meth) acrylate, and the like.

  Examples of the oligomer include epoxy (meth) acrylate, urethane (meth) acrylate, and polyester (meth) acrylate. For example, the present state and prospect of UV / EB curing technology (CMC Publishing) pages 18 to 20 are described. Can be used.

  Content of a polymeric compound (B) is a mass fraction with respect to binder resin (C) in a colored curable composition, Preferably it is 10-90 mass%, More preferably, it is 20-80 mass%. Yes, more preferably 30 to 70% by mass.

  Furthermore, the polymerizable compound (B) preferably contains a monomer or oligomer containing a carboxyl group because it tends to react with the cyclic ether structure to improve solvent resistance.

Examples of the monomer or oligomer containing a carboxyl group include an ester of a hydroxyl group-containing (meth) acrylate and a polyvalent carboxylic acid, an ester of a hydroxyl group-containing (meth) acrylate and a polyvalent carboxylic acid anhydride, and the like. It is done.
Examples of the hydroxyl group-containing polyvalent acrylate include trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate.
Examples of the polyvalent carboxylic acid include phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3 Aromatic polycarboxylic acids such as 3,3 ', 4,4'-benzophenonetetracarboxylic acid;
Aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid, itaconic acid;
Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid And alicyclic polyvalent carboxylic acids such as 1,2,4,5-cyclohexanetetracarboxylic acid.

Examples of the polyvalent carboxylic acid anhydrides include aromatic phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride. Carboxylic anhydrides;
Aliphatic polycarboxylic anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride Kind;
Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride Alicyclic polycarboxylic acid anhydrides such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic anhydride, and nadic anhydride;
Examples include ester group-containing carboxylic acid anhydrides such as ethylene glycol bistrimellitic acid and glycerin tristrimellitic anhydride.

  Specific examples of monomers or oligomers containing carboxyl groups include trimethylolpropane di (meth) acrylate phthalate, glycerin di (meth) acrylate succinate, pentaerythritol tri (meth) acrylate phthalate Examples thereof include succinic acid esters of esters, pentaerythritol triacrylate, phthalic acid esters of dipentaerythritol penta (meth) acrylate, and succinic acid esters of dipentaerythritol penta (meth) acrylate.

  When using the monomer or oligomer which has a carboxyl group as a polymeric compound (B), the content is a mass fraction with respect to polymeric compound (B), Preferably it is 1-100 mass%, More preferably, it is 5 It is -100 mass%, Most preferably, it is 10-100 mass%.

  The binder resin (C) has alkali solubility and is derived from a compound (C0) having a carbon-carbon unsaturated double bond and a cyclic ether structure (hereinafter sometimes referred to as “(C0)”). Copolymer containing a unit and a structural unit derived from at least one compound (C2) (hereinafter sometimes referred to as “(C2)”) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride It is a coalescence.

  Examples of the cyclic ether structure of (C0) include an epoxy structure, an oxetanyl structure, and a tetrahydrofuryl structure.

（式中、Ｒ^１１〜Ｒ^１３は、それぞれ独立に水素原子又は炭素原子数１〜１０のアルキル基であり、ｍは１〜５の整数である。）。 Examples of the epoxy structure include an aliphatic epoxy structure, an aliphatic monocyclic epoxy structure, and an aliphatic polycyclic epoxy structure, and an aliphatic polycyclic epoxy structure is particularly preferable.
Specific examples of the compound having a carbon-carbon unsaturated double bond and an aliphatic epoxy structure include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, and glycidyl vinyl ether. And compounds represented by the following formulas described in JP-A-7-248625.

(In formula, R < ¹¹ > -R < ¹³ > is a hydrogen atom or a C1-C10 alkyl group each independently, and m is an integer of 1-5.).

  Examples of the compound represented by the above formula include 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-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6- Diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyl Oxymethylstyrene and Include 4,6-tri-glycidyloxy-methylstyrene.

The compound having a carbon-carbon unsaturated double bond and an aliphatic monocyclic epoxy structure is a compound having an epoxy group on the ring of the aliphatic monocyclic compound.
Specific examples of the compound having a carbon-carbon unsaturated double bond and an aliphatic monocyclic epoxy structure include vinylcyclohexene monooxide 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; Daicel Chemical Industries). 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; Daicel Chemical Industries, Ltd.) Etc.).

The compound (C1) having a carbon-carbon unsaturated double bond and an aliphatic polycyclic epoxy structure (hereinafter sometimes referred to as “(C1)”) has an epoxy group on the ring of the aliphatic polycyclic compound. A compound. Examples of the aliphatic polycyclic compound include dicyclopentane and tricyclodecane.
(C1) is represented by, for example, 3,4-epoxynorbornyl acrylate, 3,4-epoxynorbornyl methacrylate, a compound represented by formula (C1-1), and formula (C1-2). A compound, preferably at least one compound selected from the group consisting of a compound represented by formula (C1-1) and a compound represented by formula (C1-2).

[In Formula (C1-1) and Formula (C1-2), R independently represents a C 1-4 alkyl group which may be substituted with a hydroxyl group or a hydrogen atom.
X represents a C1-C6 alkylene group which may contain a single bond or a hetero atom each independently. ]

Specific examples of the alkyl group having 1 to 4 carbon atoms that may be substituted with a hydroxyl group include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group. Tert-butyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxy-n-propyl group, 2-hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 1 -Hydroxy-isopropyl group, 2-hydroxy-isopropyl group, 1-hydroxy-n-butyl group, 2-hydroxy-n-butyl group, 3-hydroxy-n-butyl group, 4-hydroxy-n-butyl group, etc. Preferably a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, more preferably a methyl group. Group, and the like.
R is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.

  As a hetero atom in a C1-C6 alkylene group which may contain a hetero atom, an oxygen atom, a sulfur atom, and a nitrogen atom are mentioned. Note that the number of heteroatoms is not included in the number of carbon atoms.

Examples of the alkylene group having 1 to 6 carbon atoms which may contain a hetero atom include a methylene group, an ethylene group, a propylene group, an oxymethylene group, an oxyethylene group, an oxypropylene group, a thiomethylene group, a thioethylene group, a thiopropylene group, and an aminomethylene group. Group, aminoethylene group, aminopropylene group and the like, preferably methylene group, ethylene group, oxymethylene group or oxyethylene group, more preferably oxyethylene group.
X is preferably a single bond, a methylene group, an ethylene group, an oxymethylene group or an oxyethylene group, more preferably a single bond or an oxyethylene group.

  Examples of the compound represented by the formula (C1-1) include compounds represented by the formula (C1-1-1) to the formula (C1-1-15), preferably the formula (C1-1-1). ), Formula (C1-1-3), formula (C1-1-5), formula (C1-1-7), formula (C1-1-9), formula (C1-1-11) to formula (C1) -1-15), and more preferably a compound represented by formula (C1-1-1), formula (C1-1-7), formula (C1-1-9) or formula (C1-1). And a compound represented by 15).

  Examples of the compound represented by the formula (C1-2) include compounds represented by the formula (C1-2-1) to the formula (C1-2-15), preferably the formula (C1-2-1). ), Formula (C1-2-3), formula (C1-2-5), formula (C1-2-7), formula (C1-2-9), formula (C1-2-11) to formula (C1) -2-15), and more preferably a compound represented by formula (C1-2-1), formula (C1-2-7), formula (C1-2-9) or formula (C1-2). And a compound represented by 15).

  At least one compound selected from the group consisting of the compound represented by the formula (C1-1) and the compound represented by the formula (C1-2) can be used alone. They can also be mixed in any ratio. In the case of mixing, the mixing ratio is a molar ratio of the formula (C1-1): the formula (C1-2), preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, particularly preferably. 20:80 to 80:20.

Examples of (C2) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid;
Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
Anhydrides of the aforementioned unsaturated dicarboxylic acids;
Unsaturated mono [(meth) acryloyloxy of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Alkyl] esters;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxyl group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Among these, acrylic acid, methacrylic acid, and maleic anhydride are preferably used from the viewpoint of copolymerization reactivity and solubility in an alkaline aqueous solution. These may be used alone or in combination.

The binder resin (C) is a copolymer including a structural unit derived from (C1) and a structural unit derived from (C2), and a structural unit derived from (C1) and (C2). When the ratio of the units is a molar fraction with respect to the total number of moles of the structural units constituting the copolymer and is in the following range, storage stability, heat resistance and mechanical strength tend to be good. Therefore, it is preferable.
Structural units derived from (C1); 2-98 mol%
Structural units derived from (C2); 2-98 mol%

Moreover, it is more preferable in the point of developability and solvent resistance that the ratio of the said structural unit is the following ranges.
Structural units derived from (C1); 40 to 85 mol%
Structural unit derived from (C2); 15 to 60 mol%

The binder resin (C) is, for example, a method described in the document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972). And it can manufacture with reference to the cited reference described in the said literature.
Specifically, a predetermined amount of (C1) and (C2), a polymerization initiator, and a solvent are charged into a reaction vessel, and the oxygen is replaced with nitrogen, whereby stirring, heating, and heat retention are performed in the absence of oxygen. As a result, a copolymer is obtained. In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and took out as solid (powder) by methods, such as reprecipitation. Things may be used.

  In addition to the structural unit derived from (C1) and the structural unit derived from (C2), the binder resin (C) is a compound further copolymerizable with (C1) and (C2) (however, (C1) And (C2) are excluded.) A structural unit derived from (C3) (hereinafter sometimes referred to as “(C3)”) can be contained.

Examples of (C3) include (meth) acryl such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and tert-butyl (meth) acrylate. Acid alkyl esters;
Alkyl acrylates such as methyl acrylate and isopropyl acrylate;
Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, dicyclopenta Nyl (meth) acrylate), (meth) acrylic acid cyclic alkyl esters such as dicyclopentanyloxyethyl (meth) acrylate, isoboronyl (meth) acrylate;
Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate (commonly referred to in the art as dicyclopentanyl acrylate), dicyclo Acrylic acid cyclic alkyl esters such as pentaoxyethyl acrylate and isobornyl acrylate;
(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
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-carboxybicyclo [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-dicarboxybicyclo [2.2.1] hept-2-ene, 5,6- Di (hydroxymethyl) bicyclo [2.2.1] hept-2-e 5,6-di (2′-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6 -Diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2 .1] Hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6- Ethylbicyclo [2.2.1] hept-2-ene, 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride), 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxy Carbonyl bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (tert-butoxycarbonyl) bicyclo [2.2. 1] Bicyclo unsaturated compounds such as hept-2-ene and 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;
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 and N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid -3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl , O-Vinylbenzylglycidyl ester Ether, such as m- vinylbenzyl glycidyl ether and p- vinylbenzyl glycidyl ether. Here, in the present specification, (meth) acrylate represents at least one selected from the group consisting of acrylate and methacrylate. (Meth) acrylic acid represents at least one selected from the group consisting of acrylic acid and methacrylic acid.
Of these, benzyl acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable.
Said (C3) is used individually or in combination.

When (C3) is included, the ratio of the structural units derived from (C1) to (C3) is in the following range in terms of mole fraction with respect to the total number of moles of the structural units constituting the copolymer. And preferred.
Structural units derived from (C1); 2-97 mol%
Structural units derived from (C2); 2-97 mol%
Structural units derived from (C3); 1 to 96 mol%

  The binder resin (C) containing the above (C1) to (C3) can be produced in the same manner as described above.

  Moreover, as a structural unit in the said binder resin (C), the macromonomer which has a monoacryloyl group or a monomethacryloyl group at the terminal, the unit represented by Formula (21), the unit represented by Formula (22), etc. When it contains, it is more preferable at the point of pattern adhesiveness and solvent resistance.

(In Formula (21) and Formula (22), R ⁸ and R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

  The binder resin (C) having the structural unit represented by the formula (21) is obtained by polymerizing (C1), (C2) and (C3) to obtain a three-component copolymer, and the obtained three-component copolymer It can be obtained by reacting the union with the compound represented by the formula (23) at the carboxyl group moiety or acid anhydride group moiety contained in (C2).

  A binder resin having a constituent represented by the formula (22) is obtained by polymerizing (C1), (C2) and (C3) to obtain a three-component copolymer, and the obtained three-component copolymer; For example, glycidyl methacrylate can be obtained by reacting in the same manner as described in JP-A-2005-189574.

The polystyrene-reduced weight average molecular weight of the binder resin (C) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. If the weight average molecular weight of the binder resin (C) is in the above range, the coating property tends to be good, the film is not easily reduced during development, and the non-pixel part is easily removed during development. This is preferable because there is a certain tendency.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin (C) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. The molecular weight distribution in the above range is preferable because it tends to be excellent in developability.
Content of binder resin (C) is a mass fraction with respect to solid content in a colored curable composition, Preferably it is 10-35 mass%, More preferably, it is 15-30 mass%. When the content of the binder resin (C) is in the above range, the solubility in the developer is sufficient, development residue is hardly generated on the non-pixel portion of the substrate, and the pixel portion of the exposed portion during development. This is preferable because the film loss is less likely to occur, and the non-pixel portion is liable to be removed.

  The colored curable composition of the present invention may further contain a melamine compound and / or a guanamine compound (D). The melamine compound and the guanamine compound are not particularly limited, and known substances described in JP-A-9-166870, JP-A-10-48834, JP-A-2000-47378, JP-A-2001-242624, JP-A-2007-169607 are used. can do.

Specifically, as the melamine compound, 1 to 6 methylol groups of monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, hexamethylol melamine were methoxymethylated. Compound or a mixture thereof, a compound in which 1 to 6 methylol groups of hexamethylol melamine are ethoxymethylated or a mixture thereof, a compound in which 1 to 6 methylol groups of hexamethylol melamine are propoxymethylated, or a mixture thereof, hexamethylol melamine Examples thereof include compounds in which 1 to 6 methylol groups are butoxymethylated, or mixtures thereof.
Examples of the guanamine compound include monomethylol guanamine, dimethylol guanamine, trimethylol guanamine, tetramethylol guanamine, a compound in which 1 to 4 methylol groups of tetramethylol guanamine are methoxymethylated, or a mixture thereof, and tetramethylol guanamine 1 to 4 Compounds in which one methylol group is ethoxymethylated or a mixture thereof, compounds in which 1 to 4 methylol groups of tetramethylolguanamine are propoxymethylated or a mixture thereof, and 1 to 4 methylol groups in tetramethylolguanamine are butoxymethylated Or a mixture thereof, a compound in which 1 to 3 methoxymethyl groups of tetramethoxymethylguanamine are butoxymethylated, and the like.

The melamine compound and / or guanamine compound (D) may be used alone or in combination of two or more.
Content of a melamine compound and / or a guanamine compound (D) is a mass fraction with respect to solid content in a colored curable composition, Preferably it is 0.5-50 mass%, More preferably, it is 1-40. It is mass%, More preferably, it is 1-35 mass%.

  The colored curable composition of the present invention may further contain a thermal polymerization initiator (E). Examples of the thermal polymerization initiator (E) include organic peroxides and azo compounds, and known substances described in JP-A-9-241339, JP-A-2002-348344, JP-A-2006-013000 and the like can be used. .

  Examples of the organic peroxide include isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, α-methylbenzoyl peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, 1,1. , 3,3, -tetramethylbutyl hydroperoxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 1,3-bis (tert-butylperoxyisopropyl) benzene, dicumyl Peroxide, di-tert-butyl peroxide, paramentane hydroperoxide, tert-butyl cumyl peroxide, di-tert-hexyl peroxide, tert-butyl peroxyacetate, 2,4,4-to Methylpentylperoxyphenoxyacetate, t-butylperoxybenzoate, 2,2-di- (tert-butylperoxy) butane, di-tert-methoxybutylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate and Examples include diisopropyl peroxydicarbonate, preferably diisopropylbenzene hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5- Dimethyl-2,5-di (tert-butylperoxy) hexane, dicumyl peroxide, di-tert-butyl peroxide, paramentane hydroperoxide, tert-butylcumylperoxy Side, di-tert-hexyl peroxide, tert-butyl peroxyacetate, t-butyl peroxybenzoate or 2,2-di- (tert-butylperoxy) butane, more preferably dicumyl peroxide, Di-tert-hexyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, paramentane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3, -tetramethylbutyl hydroperoxide Or cumene hydroperoxide is mentioned.

Examples of the azo compound include 1,1′-azobiscyclohexane-1-carbonitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), and 2,2′-azobis- (2,4- Dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis- (methylisobutyrate), 2,2′-azobis- (isobutyrate) Nitrile), 4,4′-azobis- (4-cyanovaleric acid), and the like. Examples include 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis- (1-cyclohexanecarbonitrile), and the like.
These thermal polymerization initiators (E) may be used alone or in combination of two or more.

  When using a thermal-polymerization initiator (E), the content is a mass fraction with respect to binder resin (C), Preferably it is the range of 0.01-20 mass%, More preferably, it is 0.02-. The range is 10% by mass.

  The colored curable composition of the present invention may further contain a photopolymerization initiator (F). Examples of the photopolymerization initiator include triazine compounds, acetophenone compounds, biimidazole compounds, active radical generators, and acid generators.

  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- (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) ethenyl] -1,3,5-triazine, 2,4- Bis (trichloromethyl) ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine. 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- (4-methoxystyryl) -1,3,5-triazine or 2,4-bis (trichloromethyl) -6-piperonyl-1 3,5-triazine, more preferably 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and 2-hydroxy-2-methyl-1-phenylpropane-1. -One, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 2-hydroxy-2-methyl- And oligomers of 1- [4- (1-methylvinyl) phenyl] propan-1-one Preferably 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one or 2- ( 4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, more preferably 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane- 1-one or 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butan-1-one.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4, 4 ′, 5,5′-tetra (4-carboethoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (4-bromophenyl) biimidazole 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (2,4-dichlorophenyl) biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2- Chlorophenyl)- , 4 ′, 5,5′-tetra (m-methoxyphenyl) biimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2, 2′-bis (2,6-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-nitrophenyl) -4,4 ′, 5,5′- Examples thereof include tetraphenylbiimidazole and 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, preferably 2,2′-bis (2-chlorophenyl). Examples include -4,4 ', 5,5'-tetraphenylbiimidazole or 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole.

  An active radical generator generates an active radical when irradiated with light. Examples of the active radical generator include benzoin compounds, benzophenone compounds, thioxanthone compounds, and oxime compounds.

  Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butyl). Peroxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone.

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

  Examples of the oxime compounds include O-acyloxime compounds, and specific examples thereof include 1- (4-phenylsulfanyl-phenyl) -butane-1,2-dione 2-oxime-O—. Benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1,2-dione 2-oxime-O-benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1-one oxime-O-acetate And 1- (4-phenylsulfanyl-phenyl) -butan-1-one oxime-O-acetate.

  Examples of active radical generators other than those exemplified above include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, and 9,10-phenanthrenequinone. Camphorquinone, methyl phenylglyoxylate, titanocene compounds, and the like can also be used.

  Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium-p-toluenesulfonate, 4-acetoxyphenyl. Onium salts such as methylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate And benzoin tosylate.

  Among the compounds described above as the active radical generator, there are compounds that generate an acid simultaneously with the active radical. For example, a triazine photopolymerization initiator is also used as an acid generator.

  When using a photoinitiator (F), the content is a mass fraction with respect to the total amount of a polymeric compound (B) and binder resin (C), Preferably it is 0.1-25 mass%. More preferably, it is 1-20 mass%.

The colored curable composition of the present invention may further contain a photopolymerization initiation assistant (G). The photopolymerization initiation assistant (G) is usually used in combination with the photopolymerization initiator (F), and used to accelerate the polymerization of the photopolymerizable compound initiated by the photopolymerization initiator (F). Compound.
Examples of the photopolymerization initiation aid (G) include amine compounds, alkoxyanthracene compounds, and thioxanthone compounds.
Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylbenzoate. Aminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone and 4,4′-bis (Ethylmethylamino) benzophenone and the like can be mentioned, and 4,4′-bis (diethylamino) benzophenone is preferable.

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. Can be mentioned.

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

  The photopolymerization initiation assistant (G) may be used alone or in combination of two or more. Moreover, as a photopolymerization start adjuvant (G), a commercially available thing can also be used, and as a commercially available photopolymerization start adjuvant (G), it is EAB-F (Hodogaya Chemical Co., Ltd. by a brand name), for example. And 4,4′-bis (diethylamino) benzophenone) and other organic amine compounds.

  In the present invention, when the photopolymerization initiation assistant (G) is used, examples of the combination of the photopolymerization initiator (F) / photopolymerization initiation assistant (G) include 2,4-bis (trichloromethyl) -6- Piperonyl-1,3,5-triazine / 4,4′-bis (diethylamino) benzophenone, diethoxyacetophenone / 4,4′-bis (diethylamino) benzophenone, 2-methyl-2-morpholino-1- (4-methylthio Phenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one / 4,4′-bis (diethylamino) benzophenone, benzyldimethyl ketal / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydride) Xyloxy) phenyl] propan-1-one / 4,4′-bis (diethylamino) benzophenone, 1-hydroxycyclohexyl phenyl ketone / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [ 4- (1-Methylvinyl) phenyl] propan-1-one oligomer / 4,4′-bis (diethylamino) benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1- ON / 4,4′-bis (diethylamino) benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone and 2- ( 4-Methylbenzyl) -2-dimethylamino-1- (4-morpholinov Nyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone and the like, preferably 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4, 4′-bis (diethylamino) benzophenone, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine / 4,4′-bis (diethylamino) benzophenone or 2- (4-methylbenzyl) 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone.

  When using these photoinitiator adjuvant (G), the usage-amount is with respect to 1 mass part of photoinitiators (F), Preferably it is 0.01-10 mass parts, More preferably, it is 0.01-5 masses. Part.

  The colored curable composition of the present invention may further contain a solvent (H). Examples of the solvent (H) include ethers, aromatic hydrocarbons, ketones, alcohols, esters and amides.

  Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 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, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Over DOO, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, methoxybutyl acetate, methoxy pentyl acetate, anisole, phenetole, and the like methyl anisole.

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

  Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and 4-hydroxy-4-methyl-2. Examples include pentanone.

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

  Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3 -Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2- Ethyl methyl propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutane Examples include methyl acid, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and γ-butyrolactone.

  Examples of the amides include N, N-dimethylformamide and N, N-dimethylacetamide.

Examples of the other solvent (H) include N-methylpyrrolidone and dimethyl sulfoxide.
The solvents (H) may be used alone or in combination of two or more.

  The solvent (H) is preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate or diacetone alcohol.

  Content of a solvent (H) is a mass fraction with respect to a colored curable composition, Preferably it is 70-90 mass%, More preferably, it is 75-88 mass%.

  Furthermore, the colored curable composition of the present invention may contain a surfactant (I). Examples of the surfactant (I) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom.

  Examples of the silicone surfactant include surfactants having a siloxane bond. Specifically, it is a Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, 29SHPA, SH30PA, polyether-modified silicone oil SH8400 (manufactured by Torresilicone Co., Ltd.), KP321, KP322, KP323. , KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (manufactured by GE Toshiba Silicone Co., Ltd.).

  Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, under the product names Florard FC430, FC431 (Sumitomo 3M Co., Ltd.), MegaFuck F142D, F171, F172, F173, F177, F183, F470, F475, and R30 ( Dainippon Ink & Chemicals, Inc.), F-Top EF301, EF303, EF351, EF352 (made by Shin-Akita Kasei), Surflon S381, S382, SC101, SC105 (made by Asahi Glass Co., Ltd.) ), E5844 (manufactured by Daikin Fine Chemical Laboratory), BM-1000, BM-1100 (manufactured by BM Chemie), and the like.

Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specific examples include Megafax R08, BL20, F475, F477, F443 (Dainippon Ink Chemical Co., Ltd.).
These surfactants may be used alone or in combination of two or more.

  The colored curable composition of the present invention may contain an organic acid having a molecular weight of 1,000 or less. As said organic acid, the organic acid disclosed by Unexamined-Japanese-Patent No. 5-34363 is mentioned, for example. Specifically, malonic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, citraconic acid, itaconic acid, mesaconic acid, fumaric acid, phthalic acid, acrylic acid and A methacrylic acid is mentioned, Preferably malonic acid, an oxalic acid, a fumaric acid, or a phthalic acid is mentioned.

  The colored curable composition of the present invention further includes a filler, a polymer compound other than the binder resin (C), an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, an organic amine compound, a curing agent, and the like. The additive may be contained.

  Examples of the filler include fine particles such as glass and alumina.

  Examples of the polymer compound other than the binder resin (C) include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate.

  Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxymethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) Examples include ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

  Examples of the antioxidant include 4,4′-thio-bis (6-tert-butyl-3-methylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-). 4-hydroxyphenyl) propionate], 1,6-hexanediol-bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4, 6-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2,6-di-tert-butyl-4 Methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-thio-bis (3-methyl-6) -Tert-butylphenol), 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane 1,3,5-tris (4-hydroxybenzyl) benzene and tetrakis [methylene-3- (3,5′-di-tert-butyl-4′-hydroxyphenylpropionate)] methane.

Examples of the ultraviolet absorber include benzotriazoles such as 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole;
Benzophenone series such as 2-hydroxy-4-octyloxybenzophenone;
Benzoate systems such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate;
And triazines such as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol.

  Examples of the aggregation preventing agent include sodium polyacrylate.

Examples of the organic amine compound include n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n- Monoalkylamines such as octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine;
Monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine;
Methylethylamine, diethylamine, methyl-n-propylamine, ethyl-n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, Dialkylamines such as di-n-pentylamine and di-n-hexylamine;
Monoalkylmonocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine;
Dicycloalkylamines such as dicyclohexylamine;
Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, triisopropylamine, tri-n -Trialkylamines such as butylamine, triisobutylamine, tri-sec-butylamine, tri-tert-butylamine, tri-n-pentylamine, tri-n-hexylamine;
Dialkylmonocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine;
Monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine, tricyclohexylamine;
Monoalkanolamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, and 6-amino-1-hexanol Kind;
Monocycloalkanolamines such as 4-amino-1-cyclohexanol;
Dialkanolamines such as diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine;
Dicycloalkanolamines such as di (4-cyclohexanol) amine;
Trialkanolamines such as triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine;
Tricycloalkanolamines such as tri (4-cyclohexanol) amine;
3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1 Aminoalkanediols such as 1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol;
Aminocycloalkanediols such as 4-amino-1,2-cyclohexanediol and 4-amino-1,3-cyclohexanediol;
Amino group-containing cycloalkanone methanols such as 1-aminocyclopentanone methanol and 4-aminocyclopentanone methanol;
Amino group-containing cycloalkanemethanol such as 1-aminocyclohexanemethanol, 4-aminocyclohexanemethanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol;
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisoacetic acid, 3-aminoisoacetic acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclo Aminocarboxylic acids such as propanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid;
Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, p-isopropylaniline, pn-butylaniline, p-tert-butylaniline, 1- Aromatic amines such as naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-N, N-dimethylaniline;
aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol;
aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol and p-diethylaminophenol;
and aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid;

  As said hardening | curing agent, the compound etc. which can carry out ring-opening polymerization of the epoxy group in binder resin (C) by heating are mentioned, for example. Examples of the compound include polyvalent carboxylic acids and polyvalent carboxylic acid anhydrides.

Examples of the polyvalent carboxylic acids include phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3 Aromatic polycarboxylic acids such as 3,3 ', 4,4'-benzophenonetetracarboxylic acid;
Aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid, itaconic acid;
Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid And alicyclic polyvalent carboxylic acids such as 1,2,4,5-cyclohexanetetracarboxylic acid.

Examples of the polyvalent carboxylic acid anhydrides include aromatic phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride. Carboxylic anhydrides;
Aliphatic polycarboxylic anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride Kind;
Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride Alicyclic polycarboxylic acid anhydrides such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic anhydride, and nadic anhydride;
And ester group-containing carboxylic acid anhydrides such as ethylene glycol bistrimellitic acid and glycerol tristrimellitic anhydride.

  As said carboxylic acid anhydride, you may use what is marketed as an epoxy resin hardening | curing agent. Examples of the epoxy resin curing agent include ADEKA HARDNER EH-700 (manufactured by Asahi Denka Kogyo Co., Ltd.), RIKACID HH and MH-700 (both manufactured by Shin Nippon Rika Co., Ltd.). It is done.

  The above curing agents may be used alone or in combination of two or more.

  As a method of forming a color filter pattern using the colored curable composition of the present invention, for example, the colored curable composition of the present invention is first formed on a substrate or another resin layer (for example, on the substrate). Applied to another colored curable composition layer, etc.), removing a volatile component such as a solvent to form a colored layer, exposing the colored layer through a photomask, developing, and In response to this, the so-called photolithography method, in which a pattern is formed by heating, or a colored curable composition is applied to a substrate or another resin layer using an inkjet device, and a volatile component such as a solvent is removed to form a colored layer. And an ink jet method in which a pattern is formed by curing by at least one of heating and exposure.

  The color filter thus obtained contains a pattern, and a suitable liquid crystal display device can be obtained by using the color filter.

  Hereinafter, the present invention will be described in more detail with reference to examples.

Synthesis example 1
<Synthesis of Dye (A-2)>

  After adding 25 parts of water to 5.0 parts of 4-aminobenzoic acid represented by the formula (24), the pH was adjusted to 7-8 with a 30% aqueous sodium hydroxide solution under ice cooling. The following operations were performed under ice cooling. 7.6 parts of sodium nitrite was added and stirred for 30 minutes. After adding 22.8 parts of 35% hydrochloric acid little by little to give a brown solution, the mixture was stirred for 2 hours. An aqueous solution in which 6.9 parts of amidosulfuric acid was dissolved in 69 parts of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.

  To 10.5 parts of 1- (2-ethylhexyl) -3-cyano-4-methyl-6-hydroxypyrid-2-one represented by the formula (25), 105 parts of N-methylpyrrolidone and 53 parts of water 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 mixture was further stirred for 2 hours to obtain a brown suspension. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 10.9 parts (yield 73%) of the azo compound represented by the formula (10).

The structure of the azo compound (10) was determined by ¹ H-NMR, ¹³ C-NMR, and mass spectrometry. ECA-500 (manufactured by JASCO Corporation) was used as the NMR apparatus, and Agilent 1100 HP LC / MSD (manufactured by Agilent Technologies) was used as the mass spectrometer. :
¹ H-NMR (500 MHz, δ value (ppm, TMS standard), DMSO);
¹³ C-NMR (125 MHz, δ value (ppm, TMS standard), DMSO):
Mass spectrometry:
TIC = ESI +, Fr = 50 V: [M + H] m / z = 411
TIC = ESI−, Fr = 50 V: [M−H] m / z = 409

0.35 g of the obtained azo compound (10) was dissolved in ethyl lactate to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ethyl lactate 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 1.97 (arbitrary unit) at λmax = 431 nm.

Synthesis example 2
After adding 25 parts of water to 5.0 parts of 4-aminobenzoic acid represented by the formula (24), the pH was adjusted to 7-8 with a 30% aqueous sodium hydroxide solution under ice cooling. The following operations were performed under ice cooling. 7.6 parts of sodium nitrite was added and stirred for 30 minutes. After adding 22.8 parts of 35% hydrochloric acid little by little to give a brown solution, the mixture was stirred for 2 hours. An aqueous solution in which 6.9 parts of amidosulfuric acid was dissolved in 69 parts of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.

  1- [3′-propyl (2 ″ -ethylhexyloxy)]-3-cyano-4-methyl-6-hydroxypyrid-2-one represented by the formula (26) is substituted with 12.9 parts of N-methyl. After adding 129 parts of pyrrolidone and 64 parts of water, 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 brown suspension. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 12.5 parts (yield 73%) of the azo compound represented by the formula (12).

The structure of the azo compound (12) was determined by mass spectrometry. Agilent 1100 HP LC / MSD (manufactured by Agilent Technologies) was used as the mass spectrometer. :
Mass spectrometry:
TIC = ESI +, Fr = 50 V: [M + H] m / z = 469
TIC = ESI−, Fr = 50 V: [M−H] m / z = 467

0.35 g of the obtained azo compound (12) was dissolved in ethyl lactate to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ethyl lactate 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 1.89 (arbitrary unit) at λmax = 431 nm.

Synthesis example 3
<Synthesis of Resin (C-1)>
Into a 1 L 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 100 parts by mass of 3-methoxybutyl acetate were added. And heated to 70 ° C. with stirring. Next, 54 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (C1-1-1) and a formula (C1-2) The compound represented by 1) is mixed at a molar ratio of 50:50.) A solution is prepared by dissolving 180 parts by mass and 67 parts by mass of N-cyclohexylmaleimide in 140 parts by mass of 3-methoxy-1-butanol. Then, the solution was dropped into a flask kept at 70 ° C. for 4 hours using a dropping pump. On the other hand, a solution obtained by dissolving 20 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 240 parts by mass of 3-methoxybutyl acetate was added to a flask over another 4 hours using another dropping pump. It was dripped in. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C. for 4 hours, and then cooled to room temperature, and a copolymer having a solid content of 32.6% by mass and an acid value of 34.3 mg-KOH / g ( A solution of Resin C-1) was obtained. The obtained resin C-1 had a weight average molecular weight Mw of 9000 and a dispersity of 1.9.

Synthesis example 4
<Synthesis of Resin (C-2)>
Into a 1 L 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 100 parts by mass of 3-methoxybutyl acetate were added. And heated to 70 ° C. with stirring. Next, 68 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (C1-1-1) and a formula (C1-2) The compound represented by 1) is mixed at a molar ratio of 50:50.) A solution is prepared by dissolving 150 parts by mass and 82 parts by mass of styrene in 140 parts by mass of 3-methoxy-1-butanol, The solution was dropped into the flask kept at 70 ° C. over 4 hours using a dropping pump. On the other hand, a solution obtained by dissolving 20 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 240 parts by mass of 3-methoxybutyl acetate was added to a flask over another 4 hours using another dropping pump. It was dripped in. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C. for 4 hours, and then cooled to room temperature, and a copolymer having a solid content of 27.1% by mass and an acid value of 44.2 mg-KOH / g ( A solution of Resin C-2) was obtained. The obtained resin C-2 had a weight average molecular weight Mw of 7000 and a dispersity of 1.7.

Synthesis example 5
<Synthesis of Resin (C-3)>
Nitrogen was flowed at a rate of 0.02 L / min into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, 300 parts by mass of diethylene glycol methyl ethyl ether was added, and the mixture was heated to 70 ° C. with stirring. Next, 46 parts by mass of methacrylic acid, 95 parts by mass of glycidyl methacrylate, 84 parts by mass of N-cyclohexylmaleimide and 37 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) were added to diethylene glycol methyl ethyl ether 225. A solution was prepared by dissolving in parts by mass, and the solution was dropped into a flask kept at 70 ° C. over 1 hour. After completion of the dropwise addition, the mixture was kept at 70 ° C. for 4 hours and then cooled to room temperature, and a copolymer (resin C-3) having a solid content of 30.0% by mass and an acid value of 39.0 mg-KOH / g was obtained. A solution was obtained. The obtained resin A-3 had a weight average molecular weight Mw of 10,700 and a dispersity of 2.74.

Synthesis Example 6
<Synthesis of Resin (C-4)>
Into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to form a nitrogen atmosphere, and 200 parts of 3-methoxy-1-butanol and 105 parts of 3-methoxybutyl acetate were added. Heat to 70 ° C. with stirring. Next, 60 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (C1-1-1) and formula (C1-2-1) The compound represented by) is mixed at a molar ratio of 50:50.) A solution is prepared by dissolving in 240 parts and 140 parts of 3-methoxybutyl acetate. Over time, it was dripped in the flask kept at 70 degreeC. On the other hand, a solution prepared by dissolving 30 parts of polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 90 parts of 3-methoxy-1-butanol and 135 parts of 3-methoxybutyl acetate was added to another dropping funnel. Was dropped into the flask over 4 hours. After completion of dropping 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 7.5 × 10 ³ , the degree of dispersion was 2.5, and the solid content was A solution of a copolymer (resin C-4) having 33% and an acid value of 34 mg-KOH / g was obtained.

About the measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the said binder resin, it carried out on condition of the following using GPC method.
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
The ratio of the weight-average molecular weight and number-average molecular weight obtained above in terms of polystyrene was defined as the degree of dispersion (Mw / Mn).

(A-1) Dye: Compound represented by formula (5) (Neptun Yellow 075: manufactured by BASF)
(A-2) Dye: Compound represented by Formula (10) obtained in Synthesis Example 1 (A-3) Dye: Compound pigment dispersion represented by Formula (12) obtained in Synthesis Example 2: C. I. 14 parts of Pigment Green 58 and 3.4 parts of an acrylic pigment dispersant were mixed with 82.6 parts of propylene glycol monomethyl ether acetate, and a pigment dispersion liquid (B- 1) Photopolymerizable compound: Kayalad DPHA (Nippon Kayaku Co., Ltd .: mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
(B-2) Photopolymerizable compound: TO-2349 (manufactured by Shin-Nakamura Chemical Co., Ltd .: mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate and succinic acid derivative of dipentaerythritol pentaacrylate, acid Value 67.8 mg KOH / g)
(C-1) Binder resin: Resin (C-1) obtained in Synthesis Example 3 (solid content: 32.6% by mass)
(C-2) Binder resin: Resin (C-2) obtained in Synthesis Example 4 (solid content: 27.1% by mass)
(C-3) Binder resin: Resin (C-3) obtained in Synthesis Example 5 (solid content: 30.0% by mass)
(C-4) Binder resin: Resin (C-4) obtained in Synthesis Example 6 (solid content: 33.0% by mass)
(F-1) Photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (F-2) photopolymerization initiator: 2,4-bis (trichloromethyl) ) -6-piperonyl-1,3,5-triazine (G-1) photopolymerization initiation assistant: 4,4′-bis (diethylamino) benzophenone (H-1) Solvent: propylene glycol monomethyl ether (H-2) Solvent: Ethyl 3-ethoxypropionate (I-1) Surfactant: Megafac F475 (manufactured by Dainippon Ink & Chemicals, Inc.)

Example 1
[Preparation of colored curable composition 1]
(A-1) 40.6 parts by mass (B-1) 21.8 parts by mass (C-1) 83.4 parts by mass (solid content conversion value: 27.2 parts by mass)
(F-1) 8.9 parts by mass (G-1) 1.5 parts by mass (H-1) 334.8 parts by mass (H-2) 16.7 parts by mass (I-1) 0.004 parts by mass Were mixed to obtain a colored curable composition 1.

[Formation of coating film 1]
Next, on the glass (# 1737; manufactured by Corning), the colored curable composition 1 obtained above was applied by a spin coating method, and then the volatile components were volatilized at 100 ° C. for 3 minutes to form a colored curable composition film. Formed. After cooling, the colored curable composition film was exposed to i-line (wavelength 365 nm) for exposure. An ultra-high pressure mercury lamp was used as the i-line light source, and the light was irradiated after being converted into parallel light. The amount of irradiation light was 500 mJ / cm ² . Subsequently, post-baking was performed at 220 ° C. for 20 minutes to obtain a colored curable composition film having a thickness of 2 μm.

[Evaluation 1] Solvent resistance evaluation 1
The chromaticity of the obtained colored curable composition film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS).
Next, the obtained colored curable composition film was immersed in a large excess amount of propylene glycol monomethyl ether kept at 23 ° C. for 30 minutes, and the chromaticity of the colored curable composition film after immersion was similarly set. When measured and the color difference before and after immersion was determined, ΔEab * = 1.8.
As an evaluation standard for color difference, if ΔEab * is 5 or less, almost no hue change is observed, showing good characteristics as a color filter, and if ΔEab * is more than 5 and less than 10, slight hue change is recognized. However, if the color filter has a practically no problem level and ΔEab * is 10 or more, a clear hue change can be confirmed, which is a problematic level for the color filter.

[Evaluation 2] Solvent resistance evaluation 2
The chromaticity of the obtained colored curable composition film was measured using the same colorimeter as described above.
Next, the obtained colored curable composition film was immersed in a large excess amount of N-methyl-2-pyrrolidone maintained at 23 ° C. for 30 minutes, and the chromaticity of the colored curable composition film after immersion was determined. It measured similarly and the color difference before and behind immersion was calculated | required, it was (DELTA) Eab * = 6.5.

[Formation of coating film 2]
On the glass (# 1737; manufactured by Corning), the colored curable composition 1 obtained above is applied by spin coating, and then the volatile components are volatilized at 100 ° C. for 3 minutes to form a colored curable composition film. did. After cooling, the colored curable composition film was exposed by irradiating with i-line (wavelength 365 nm) through a photomask. An ultra-high pressure mercury lamp was used as the i-line light source, and the light was irradiated after being converted into parallel light. The amount of irradiation light was 500 mJ / cm ² . As the photomask, a photomask for forming linear color pixels having line widths of 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, and 100 μm was used.
Next, the film is dipped in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 25 ° C. for 60 seconds, developed, washed with pure water, and a line and space pattern is formed. A tempered glass substrate was obtained.

[Evaluation 3] Development residue evaluation When the spectral spectrum of the non-exposed portion of the glass substrate patterned with the line-and-space pattern obtained by the above operation was measured using the same colorimeter as described above, the light of wavelength 550 nm was measured. The transmittance was 99.98%.
As an evaluation standard for the development residue, when the light transmittance at a wavelength of 550 nm is 99.90% or more, the development residue is hardly recognized, and the color filter exhibits good characteristics, and the light transmittance at a wavelength of 550 nm is 99. If it is less than 90%, it is a problematic level as a color filter.

Examples 2-6
Colored curable compositions 2 to 6 were obtained in the same manner as in Example 1 except that the composition of the components of the colored curable composition was changed as shown in Table 1.
Table 2 shows the results of evaluating the obtained colored curable compositions 2 to 6 in the same manner as in Example 1.

  According to the colored curable composition of this invention, the pattern excellent in solvent resistance can be formed.

Claims (9)

Containing dye (A), polymerizable compound (B), binder resin (C),
The binder resin (C) is selected from the group consisting of a structural unit derived from the compound (C0) having a carbon-carbon unsaturated double bond and a cyclic ether structure, and an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. A colored curable composition comprising a copolymer containing a structural unit derived from at least one compound (C2).   The colored curable composition according to claim 1, wherein the cyclic ether structure is an aliphatic polycyclic epoxy structure. The compound (C0) having a carbon-carbon unsaturated double bond and a cyclic ether structure is at least selected from the group consisting of a compound represented by the formula (C1-1) and a compound represented by the formula (C1-2). The colored curable composition according to claim 1, which is one kind of compound.

[In Formula (C1-1) and Formula (C1-2), R independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom which may be substituted with a hydroxyl group.
X represents a C1-C6 alkylene group which may contain a single bond or a hetero atom each independently. ]   The colored curable composition according to any one of claims 1 to 3, wherein the dye (A) is a dye containing a dye having a carboxyl group.   The colored curable composition according to claim 1, wherein the polymerizable compound (B) is a monomer or oligomer having a carboxyl group.   Furthermore, the coloring curable composition in any one of Claims 1-5 containing a pigment.   The pattern formed by the photolithographic method or the inkjet method using the colored curable composition in any one of Claims 1-6.   A color filter comprising the pattern according to claim 7.   A liquid crystal display device comprising the color filter according to claim 8.