JP2021152145A - Colored curable resin composition - Google Patents

Abstract

To provide a colored curable resin composition that can form a color filter that is thin while having a deep color.SOLUTION: A colored curable resin composition contains a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), the polymerizable compound (C) containing a first compound of formula (1) and a second compound of formula (2). [In formula (1), at least one of R1a-R3a is a hydrogen atom and the remainder independently represent a (meth)acryloyl group.] [In the formula (2), R1b-R3b independently represent a (meth)acryloyl group.]SELECTED DRAWING: None

Description

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

Color filters used in display devices such as liquid crystal displays, electroluminescence display devices and plasma displays, and solid-state image sensors such as CCDs and CMOS sensors are manufactured from colored curable resin compositions.

Conventionally, examples of using ethylene oxide glycerin triacrylate as a polymerizable compound used in a color curable resin composition (see, for example, Patent Document 1), dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate Examples of using a mixture (see, for example, Patent Document 2) and the like are known.

Japanese Unexamined Patent Publication No. 2008-164886 Japanese Unexamined Patent Publication No. 2019-11494

By the way, in recent years, there has been an increasing demand for display devices and solid-state image sensors having a wide color gamut and good color reproducibility, and there is a demand for a color filter having a dark color and a thin film. However, in the conventional color curable resin composition, there is still room for consideration of thinning in the production of a dark color filter. Therefore, it is an object of the present invention to provide a color curable resin composition capable of forming a thin film color filter while having a dark color.

［式（１）中、Ｒ^1a〜Ｒ^3aのいずれか１つは水素原子を表し、残りはそれぞれ独立に、（メタ）アクリロイル基を表す。］

［式（２）中、Ｒ^1b〜Ｒ^3bは、それぞれ独立に、（メタ）アクリロイル基を表す。］
［２］ 第１化合物と第２化合物の質量比（第１化合物／第２化合物）が、５／９５〜９３／７である［１］に記載の着色硬化性樹脂組成物。
［３］ 前記重合性化合物（Ｃ）が、さらに式（３）で表される第３化合物を有していてもよく、
第１化合物、第２化合物、及び第３化合物の合計１００質量％中、第１化合物の含有量が５〜７５質量％であり、第２化合物の含有量が５〜９５質量％であり、第３化合物の含有量が０〜２０質量％である［１］または［２］に記載の着色硬化性樹脂組成物。

［式（３）中、Ｒ^1c〜Ｒ^3cのいずれか２つは水素原子を表し、残りは（メタ）アクリロイル基を表す。］
［４］ 膜厚が２．００μｍ以下であり、かつＣ光源を使用して測色した際のＣＩＥのＸＹＺ表色系における色度座標が、ｘ＝０．１７０〜０．３００、ｙ＝０．６００〜０．８００の範囲にある硬化膜を形成可能な、［１］〜［３］のいずれか１項に記載の着色硬化性樹脂組成物。
［５］ 膜厚が２．００μｍ未満であり、かつＣ光源を使用して測色した際のＣＩＥのＸＹＺ表色系における色度座標が、ｘ＝０．６４０〜０．７１０、ｙ＝０．２９０〜０．３３０の範囲にある硬化膜を形成可能な、［１］〜［３］のいずれか１項に記載の着色硬化性樹脂組成物。
［６］ 膜厚が２．００μｍ未満であり、かつＣ光源を使用して測色した際のＣＩＥのＸＹＺ表色系における色度座標が、ｘ＝０．１３０〜０．１６０、ｙ＝０．０３５〜０．０８０の範囲にある硬化膜を形成可能な、［１］〜［３］のいずれか１項に記載の着色硬化性樹脂組成物。
［７］ ［１］〜［６］のいずれか１項に記載の着色硬化性樹脂組成物から形成されるカラーフィルタ。
［８］ ［７］に記載のカラーフィルタを含む有機ＥＬ表示装置。
［９］ ［７］に記載のカラーフィルタを含むフレキシブルディスプレイ。 The gist of the present invention is as follows.
[1] Contains a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E).
A colored curable resin composition in which the polymerizable compound (C) contains a first compound represented by the formula (1) and a second compound represented by the formula (2).

[In formula (1), ^{any one of R 1a to} R ^3a represents a hydrogen atom, and the rest independently represent a (meth) acryloyl group. ]

[In formula (2), R ^{1b to} R ^3b each independently represent a (meth) acryloyl group. ]
[2] The colored curable resin composition according to [1], wherein the mass ratio of the first compound to the second compound (first compound / second compound) is 5/95 to 93/7.
[3] The polymerizable compound (C) may further have a third compound represented by the formula (3).
The content of the first compound is 5 to 75% by mass, the content of the second compound is 5 to 95% by mass, and the content of the first compound is 5 to 95% by mass in the total of 100% by mass of the first compound, the second compound, and the third compound. 3. The colored curable resin composition according to [1] or [2], wherein the content of the compound is 0 to 20% by mass.

[In formula (3), ^{any two of R 1c to} R ^3c represent hydrogen atoms, and the rest represent (meth) acryloyl groups. ]
[4] The chromaticity coordinates in the XYZ color system of CIE when the film thickness is 2.00 μm or less and the color is measured using the C light source are x = 0.170 to 0.300, y = 0. The colored curable resin composition according to any one of [1] to [3], which can form a cured film in the range of 600 to 0.800.
[5] The chromaticity coordinates in the XYZ color system of CIE when the film thickness is less than 2.00 μm and the color is measured using the C light source are x = 0.640 to 0.710, y = 0. The colored curable resin composition according to any one of [1] to [3], which can form a cured film in the range of 290 to 0.330.
[6] The chromaticity coordinates in the XYZ color system of CIE when the film thickness is less than 2.00 μm and the color is measured using the C light source are x = 0.130 to 0.160, y = 0. The colored curable resin composition according to any one of [1] to [3], which can form a cured film in the range of .035 to 0.080.
[7] A color filter formed from the colored curable resin composition according to any one of [1] to [6].
[8] An organic EL display device including the color filter according to [7].
[9] A flexible display including the color filter according to [7].

According to the color curable resin composition of the present invention, it is possible to provide a thin-film color filter while having a dark color.

<Coloring curable resin composition>
The color-curable resin composition of the present invention contains the colorant (A), the resin (B), the polymerizable compound (C), the polymerization initiator (D), and the solvent (E), and the polymerizable compound (C). ) Is the first compound represented by the formula (1) (hereinafter, may be referred to as glycerindi (meth) acrylate) and the second compound represented by the formula (2) (hereinafter, glycerin tri (meth) acrylate). In some cases), it is characterized by including.

In addition, in this specification, "(meth) acrylate" represents at least one selected from the group consisting of acrylate and methacrylate. Notations such as "(meth) acrylic acid" and "(meth) acryloyl" have the same meaning. Further, in the present specification, the compounds exemplified as each component may be used alone or in combination of a plurality of types unless otherwise specified.

<Colorant (A)>
The colorant (A) may be either a dye or a pigment, but preferably contains a pigment. As the pigment, known pigments can be used, and examples thereof include pigments classified as pigments by the Color Index (The Society of Dyers and Colorists Publishing).

Specifically, 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, 129, 137, 138, Yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214;
C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, Red pigments such as 269 and 273;
C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments;
C. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other violet color pigments;
C. I. Pigment Green 7, 36, 58, 59 green pigments;
C. I. Pigment brown 23, 25 and other brown pigments;
C. I. Examples thereof include black pigments such as Pigment Black 1 and 7.

Further, as the pigment, a compound represented by the formula (x) may be used.

When forming red pixels C.I. I. Pigment Red 254 and C.I. I. Pigment Red 177 Combination; C.I. I. Pigment Red 254, C.I. I. Pigment Red 177 and C.I. I. Pigment Yellow 150 Combination; C.I. I. Pigment Red 254, C.I. I. Pigment Red 242 and C.I. I. Pigment Yellow 150 Combination; C.I. I. Pigment Red 254 and C.I. I. Combination of Pigment Orange 38; C.I. I. Pigment Red 254, C.I. I. Pigment Red 177 and C.I. I. Pigment Yellow 138 combination; C.I. I. Pigment Red 254, C.I. I. Pigment Red 177 and C.I. I. Pigment Yellow 139 combination; C.I. I. Pigment Red 269, C.I. I. Pigment Yellow 139, C.I. I. Pigment Violet 19 combinations; etc. are preferably used.

When forming green pixels, C.I. I. Pigment Green 59, C.I. I. Pigment Yellow 138, and C.I. I. Pigment Yellow 150 Combination; C.I. I. Pigment Green 59, C.I. I. Pigment Yellow 139, and C.I. I. Pigment Yellow 185 combination; C.I. I. Pigment Green 58, C.I. I. Pigment Yellow 138, and C.I. I. Pigment Yellow 150 Combination; C.I. I. Pigment Green 58 and C.I. I. Pigment Yellow 150 Combination; C.I. I. Pigment Green 58 and C.I. I. Pigment Yellow 138 combination; C.I. I. Pigment Green 59 and C.I. I. Pigment Yellow 150 Combination; C.I. I. Pigment Green 59 and C.I. I. Pigment Yellow 138 combination; C.I. I. Pigment Green 59, C.I. I. Pigment Green 58, and C.I. I. Pigment Yellow 138 combination; C.I. I. Pigment Green 59, C.I. I. Pigment Green 58, and C.I. I. Pigment Yellow 150 Combination; C.I. I. Pigment Green 59, C.I. I. Pigment Green 58, C.I. I. Pigment Yellow 150 and C.I. I. It is preferable to use a combination of Pigment Yellow 138; etc.

When forming blue pixels, C.I. I. Pigment Blue 15: 6 and compound (x) combination; C.I. I. Pigment Blue 15: 6 and C.I. I. It is preferable to use a combination of Pigment Violet 23; etc.

If necessary, the pigment is treated with a rosin, a surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, a graft treatment on the pigment surface with a polymer compound or the like, and atomization by a sulfuric acid atomization method or the like. Treatment, cleaning treatment with an organic solvent, water, etc. for removing impurities, removal treatment of ionic impurities by an ion exchange method, or the like may be performed.
The pigment preferably has a uniform particle size. Further, by carrying out the dispersion treatment by incorporating a pigment dispersant, it is possible to obtain a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. Pigment dispersants include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Lubrizol), EFKA (manufactured by CIBA), and Ajinomoto Fine-Techno. (Manufactured by Co., Ltd.), Disperbyk (manufactured by Big Chemie), and the like.

When a pigment dispersant is used, the amount used is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less with respect to the total amount of the pigment. When the amount of the pigment dispersant used is in the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.

The content of the pigment in the colorant (A) is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and particularly preferably 95% by mass or more, 100% by mass. It may be% by mass.

The colorant (A) may contain a dye. The dye is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of the dye include compounds classified by the Color Index (The Society of Dyers and Colorists) as having a hue other than pigments, and known dyes described in dyeing notes (Color Dyeing Co., Ltd.). Be done. According to the chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acrydin dye, styryl dye, coumarin. Examples include dyes, quinoline dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

Specifically, C.I. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189;
C. I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86;
C. I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;
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 dye,
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, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176,182,183,195,198,206,211,215,216,217,227,228,249,252,257,258,260,261,266,268,270, 274,277,280,281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;
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, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;
C. I. Acid Blue 1,3,5,7,9,11,13,15,17,18,22,23,24,25,26,27,29,34,38,40,41,42,43,45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90: 1, 91, 92, 93, 93: 1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;
C. I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50: 1, 58, 63, 65, 80, C.I., 104, 105, 106, 109, etc. I. Acid dye,
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 26, 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, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;
C. I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like. I. Direct dye,
C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse Violet 26, 27;
C. I. Disperse Blue 1, 14, 56, 60, etc. I. Disperse dye,
C. I. Basic Red 1, 10;
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, 81, 83, 88, 89;
C. I. Basic Violet 2;
C. I. Basic Red 9;
C. I. Basic Green 1 etc. C.I. I. Basic dye,
C. I. Reactive Yellow 2,76,116;
C. I. Reactive orange 16;
C. I. C. of Reactive Red 36 etc. I. Reactive dye,
C. I. Modant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern tread 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38 , 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;
C. I. Modant 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, 1: 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28 , 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58;
C. I. Modant 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. Modant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53, etc. I. Mordant dye,
C. I. Bat Green 1 etc. C.I. I. Vat dyes and the like can be mentioned.

The content of the dye in the colorant (A) is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 10% by mass or less, particularly preferably 5% by mass or less, and 0. It may be% by mass.

The content of the colorant (A) is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, still more preferably 10 with respect to the total solid content of the color curable resin composition. ~ 50% by mass. When the content of the colorant (A) is within the above range, the color density when used as a color filter is sufficient, and the composition contains a required amount of the resin (B) and the polymerizable compound (C). Therefore, it is possible to form a pattern having sufficient mechanical strength.

The "total amount of solids" in the present specification means an amount obtained by subtracting the solvent content from the total amount of the colored curable resin composition. The total amount of solids and the content of each component relative to the total amount can be measured by a known analytical means such as liquid chromatography or gas chromatography.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].
Resin [K1]; a structural unit derived from at least one (a) (hereinafter sometimes referred to as “(a)”) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and 2 carbon atoms. A copolymer having a cyclic ether structure of ~ 4 and a structural unit derived from a monomer (b) having an ethylenically unsaturated bond (hereinafter, may be referred to as “(b)”);
Resin [K2]; Structural unit derived from (a), structural unit derived from (b), and monomer (c) copolymerizable with (a) (however, (a) and (b) are Different.) (Hereinafter sometimes referred to as “(c)”), a copolymer having a structural unit derived from;
Resin [K3]; a copolymer having a structural unit derived from (a) and a structural unit derived from (c);
Resin [K4]; A copolymer having a structural unit derived from (a) plus (b) and a structural unit derived from (c);
Resin [K5]; A copolymer having a structural unit derived from (b) with (a) added and a structural unit derived from (c);
Resin [K6]; A copolymer having a structural unit derived from (c) and a structural unit derived from (b) with (a) added and a carboxylic acid anhydride further added.

Specifically, as (a), 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-cyclohexendicarboxylic 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 [2.2.1] Bicyclounsaturated compounds containing a carboxy group such as hept-2-ene and 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] ester of a polyvalent carboxylic acid having a divalent value or higher, such as monooxalate [2- (meth) acryloyloxyethyl] and mono [2- (meth) acryloyloxyethyl] phthalate. Kind;
Unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid; and the like.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the obtained resin in an alkaline aqueous solution.

(B) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxylan ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. say. In (b), a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group is preferable.

Examples of (b) include a monomer (b1) having an oxylanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a simple monomer having an oxetanyl group and an ethylenically unsaturated bond. Examples include a metric (b2) (hereinafter sometimes referred to as "(b2)") and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"). Be done.

As (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”). ), Monomers (b1-2) having an alicyclic unsaturated hydrocarbon epoxidized structure (hereinafter, may be referred to as “(b1-2)”).

Examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and 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-tris (Glysidyloxymethyl) styrene and the like can be mentioned.

Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, celloxide 2000; manufactured by Daicel Co., Ltd.), and 3,4-epoxycyclohexylmethyl (meth) acrylate (for example,). Cyclomer A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Co., Ltd.), a compound represented by the formula (I) and a compound represented by the formula (II). Examples thereof include compounds represented by.

[In formulas (I) and (II), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. You may.
X ^a and X ^b is a single ^{bond, * - R c -, *} - R c -O -, * - represents the R ^c -S- or * -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, a tert-butyl group and the like.
The alkyl groups in which the hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group and 1-hydroxy. Examples thereof include -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group and 4-hydroxybutyl group.
Examples of R ^a and R ^b include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

The alkanediyl group includes a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-. Examples include 1,6-diyl group.
Examples of X ^a and X ^b are preferably a single bond, a methylene group, an ethylene group, * -CH _2- O- and * -CH ₂ CH _2- O-, and more preferably a single bond, * -CH ₂ CH _2- O-can be mentioned (* represents a bond with O).

Examples of the compound represented by the formula (I) include compounds represented by any of the formulas (I-1) to (I-15). Among them, 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 the formula (I-1), the formula (I-7), the formula (I-9) or the compound represented by the formula (I-15) is more preferable.

Examples of the compound represented by the formula (II) include compounds represented by any of the formulas (II-1) to (II-15). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15). The compound represented by the formula (II-1), the formula (II-7), the formula (II-9) or the compound represented by the formula (II-15) is more preferable.

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of two or more. When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, the content ratio thereof [the compound represented by the formula (I): the compound represented by the formula (II)] is On a molar basis, it is preferably 5:95 to 95: 5, more preferably 20:80 to 80:20.

As (b2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacrylloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, and 3-ethyl-3-acryloyloxymethyloxetane. , 3-Methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane and the like.

As (b3), a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (b), (b1) is preferable in that the reliability of the obtained color filter such as heat resistance and chemical resistance can be further improved. Further, (b1-2) is more preferable in that the color-curable resin composition has excellent storage stability.

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} ] Decane-8-yl (meth) acrylate (In the art, it is commonly referred to as "dicyclopentanyl (meth) acrylate" and may also be referred to as "tricyclodecyl (meth) acrylate". ), Tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth) acrylate (in the art, it is commonly referred to as "dicyclopentenyl (meth) acrylate"), Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) ) (Meta) acrylic acid esters such as 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, and diethyl itaconic acid;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-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 [2.2.1] 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 (cyclohexyl) Bicyclounsaturated compounds such as oxycarbonyl) bicyclo [2.2.1] hept-2-ene;
N-Phenylmaleimide, N-Cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylnitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Of these, 2-hydroxyethyl (meth) acrylate, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo [2.2. 1] Hept-2-ene, 2-ethylhexyl (meth) acrylate and the like are preferable.

In the resin [K1], the ratio of the structural units derived from each is determined in the total structural units constituting the resin [K1].
Structural unit derived from (a); 2-60 mol%
Structural unit derived from (b); 40-98 mol%
Is preferable,
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (b); 50-90 mol%
Is more preferable.
When the ratio of the structural units of the resin [K1] is within the above range, the storage stability of the color curable resin composition, the developability when forming a color pattern, and the solvent resistance of the obtained color filter are excellent. Tend.

Resin [K1] can be used, for example, in the method described in the document "Experimental Method for Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972). It can be manufactured with reference to the cited references described in.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent and the like are placed in a reaction vessel, and for example, oxygen is replaced with nitrogen to create a deoxidized atmosphere, and the mixture is stirred. Examples thereof include a method of heating and keeping warm. The polymerization initiator, solvent, and the like used here are not particularly limited, and those usually used in the art can be used. For example, as the polymerization initiator, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) or an organic peroxide (benzoyl peroxide, etc.) As the solvent, any solvent may be used as long as it dissolves each monomer, and examples of the solvent (E) of the colored curable resin composition of the present invention include a solvent described later.

As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or the copolymer is taken out as a solid (powder) by a method such as reprecipitation. You may use the one. In particular, by using the solvent contained in the color curable resin composition of the present invention as a solvent during this polymerization, the solution after the reaction can be used as it is for the preparation of the color curable resin composition of the present invention. Therefore, the manufacturing process of the colored curable resin composition of the present invention can be simplified.

In the resin [K2], the ratio of the structural units derived from each is determined in the total structural units constituting the resin [K2].
Structural unit derived from (a); 2-45 mol%
Structural unit derived from (b); 2-95 mol%
Structural unit derived from (c); 1-65 mol%
Is preferable,
Structural unit derived from (a); 5-40 mol%
Structural unit derived from (b); 5-80 mol%
Structural unit derived from (c); 5-60 mol%
Is more preferable.
When the ratio of the structural units of the resin [K2] is within the above range, the storage stability of the color-curable resin composition, the developability when forming a color pattern, and the solvent resistance of the obtained color filter, It tends to have excellent heat resistance and mechanical strength.

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

In the resin [K3], the ratio of the structural units derived from each is determined among all the structural units constituting the resin [K3].
Structural unit derived from (a); 2-60 mol%
Structural unit derived from (c); 40-98 mol%
Is preferable,
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (c); 50-90 mol%
Is more preferable.

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

The resin [K4] is a carboxylic acid and / or a carboxylic acid anhydride having the cyclic ether having 2 to 4 carbon atoms of (b) obtained by obtaining a copolymer of (a) and (c). It can be manufactured by adding to.
First, the copolymer of (a) and (c) is produced in the same manner as the method described as the method for producing the resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same as that mentioned in the resin [K3].

Next, the cyclic ether having 2 to 4 carbon atoms of (b) is reacted with a part of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer.
Following the production of the copolymer of (a) and (c), the atmosphere in the flask was replaced with air from nitrogen, and (b), a reaction catalyst of carboxylic acid or carboxylic acid anhydride and cyclic ether (for example, Tris (for example, Tris). Resin [K4] can be produced by putting (dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (for example, hydroquinone, etc.) in a flask and reacting at 60 to 130 ° C. for 1 to 10 hours, for example. can.
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, based on 100 mol of (a). Within this range, the storage stability of the colored curable resin composition, the developability when forming a pattern, and the balance between the solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained pattern are improved. Tend. Since the reactivity of the cyclic ether is high and the unreacted (b) is unlikely to remain, (b1) is preferable as the (b) used for the resin [K4], and (b1-1) is further preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c).
The reaction conditions such as the charging method, the reaction temperature and the time can be appropriately adjusted in consideration of the production equipment, the calorific value due to the polymerization and the like. As with the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the calorific value of the polymerization, and the like.

As the first step, the resin [K5] obtains a copolymer of (b) and (c) in the same manner as in the above-mentioned production method of the resin [K1]. In the same manner as above, the obtained copolymer may be a solution after the reaction as it is, a concentrated or diluted solution may be used, or a solid (powder) may be used by a method such as reprecipitation. You may use the one taken out as.
The ratio of the structural units derived from (b) and (c) is, respectively, with respect to the total number of moles of all the structural units constituting the copolymer.
Structural unit derived from (b); 5 to 95 mol%
Structural unit derived from (c); 5 to 95 mol%
Is preferable,
Structural unit derived from (b); 10-90 mol%
Structural unit derived from (c); 10-90 mol%
Is more preferable.

Further, under the same conditions as the method for producing the resin [K4], the carboxylic acid or carboxylic acid anhydride of (a) is added to the cyclic ether derived from (b) of the copolymer of (b) and (c). The resin [K5] can be obtained by reacting an object.
The amount of (a) used to react with the copolymer is preferably 5 to 80 mol with respect to 100 mol of (b). Since the reactivity of the cyclic ether is high and the unreacted (b) is unlikely to remain, (b1) is preferable as the (b) used for the resin [K5], and (b1-1) is further preferable.

The resin [K6] is a resin obtained by further reacting the resin [K5] with a carboxylic acid anhydride. The carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or the carboxylic acid anhydride.
Examples of the carboxylic acid anhydride include maleic anhydride, citraconic acid anhydride, itaconic acid anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 , 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride and the like. The amount of the carboxylic acid anhydride used is preferably 0.5 to 1 mol with respect to 1 mol of the amount used in (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxytricyclo [5.2.1.0 ^2,6. ] Resins such as decyl acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) ) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decylacrylate / (meth) acrylic acid / N-cyclohexyl maleimide copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] Decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide / 2-hydroxyethyl (meth) acrylate copolymer, 3,4-epoxytricyclo [5.2. 1.0 ^2,6 ] decyl acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate / (meth) acrylic acid / Resins such as 2-ethylhexyl (meth) acrylic acid copolymer, 3-methyl-3- (meth) acrylic loyloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate / Resin [K3] such as (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer; glycidyl (meth) acrylate was added to the benzyl (meth) acrylate / (meth) acrylic acid copolymer. Resin, tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer to which glycidyl (meth) acrylate is added, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic Resin such as resin in which glycidyl (meth) acrylate is added to an acid copolymer [K4]; Resin in which (meth) acrylic acid is reacted with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate. , A resin such as a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate with (meth) acrylic acid [K5]; tricyclodecyl (meth) acrylate / glycidyl (meth). A resin obtained by reacting a copolymer of acrylate with (meth) acrylic acid and further reacting with tetrahydrophthalic acid anhydride, etc. Resin [K6] and the like.
Among them, as the resin (B), the resin [K1] and the resin [K2] are preferable, and the resin [K2] is particularly preferable.

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 even more preferably 5,000 to 30,000. .. 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 developing solution is good, and the resolution of the coloring pattern tends to be improved.

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

The acid value of the resin (B) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 160 mg-KOH / g, and even more preferably 70 to 150 mg-KOH / g in terms of solid content. be. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be obtained by titration using, for example, an aqueous potassium hydroxide solution. ..

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to the total amount of solids. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and residual film ratio of the colored pattern tend to be improved.

<Polymerizable compound (C)>
The polymerizable compound (C) contains a first compound (glycerin di (meth) acrylate) represented by the formula (1).

［式（１）中、Ｒ^1a〜Ｒ^3aのいずれか１つは水素原子を表し、残りはそれぞれ独立に、（メタ）アクリロイル基を表す。］

[In formula (1), ^{any one of R 1a to} R ^3a represents a hydrogen atom, and the rest independently represent a (meth) acryloyl group. ]

As the first compound, a compound in which R ^2a in the formula (1) represents a hydrogen atom and R ^1a and R ^3a independently represent a (meth) acryloyl group (glycerin-1,3-di (meth) acrylate). ^{R 2a} in the formula (1) represents a hydrogen atom, and R ^1a and R ^3a are more preferably compounds (glycerin-1,3-diacrylate) representing an acryloyl group.

Further, in the glycerin-1,3-di (meth) acrylate, R ^3a in the formula (1) represents a hydrogen atom, and R ^1a and R ^2a independently represent a (meth) acryloyl group (glycerin-1). , 2-Di (meth) acrylate) may be mixed.

The polymerizable compound (C) contains a second compound (glycerin tri (meth) acrylate) represented by the formula (2) in addition to the first compound.

［式（２）中、Ｒ^1b〜Ｒ^3bは、それぞれ独立に、（メタ）アクリロイル基を表す。］

[In formula (2), R ^{1b to} R ^3b each independently represent a (meth) acryloyl group. ]

As the second compound, ^{it is preferable that R 1b to} R ^3b are compounds representing an acryloyl group (glycerin triacrylate).

The mass ratio of the first compound to the second compound (first compound / second compound) is preferably 5/95 to 93/7, more preferably 20/80 to 90/10, and even more preferably 40 /. It is 60 to 85/15, particularly preferably 50/50 to 80/20. In other words, the content of the first compound is preferably 5% by mass or more and 93% by mass or less, more preferably 20% by mass or more and 90% by mass, based on 100% by mass of the total of the first compound and the second compound. Hereinafter, it is more preferably 40% by mass or more and 85% by mass or less, particularly preferably 50% by mass or more and 80% by mass or less, and the content of the second compound is 7% by mass or more and 95% by mass or less. It is preferably 10% by mass or more and 80% by mass or less, more preferably 15% by mass or more and 60% by mass or less, and particularly preferably 20% by mass or more and 50% by mass or less. By adjusting the mass ratio of the first compound and the second compound within the above range, it is possible to reduce the film thickness of the obtained cured film.

The polymerizable compound (C) further contains a third compound represented by the formula (3) (hereinafter, may be referred to as glycerin mono (meth) acrylate) in addition to the first compound and the second compound. You may.

［式（３）中、Ｒ^1c〜Ｒ^3cのいずれか２つは水素原子を表し、残りは（メタ）アクリロイル基を表す。］

[In formula (3), ^{any two of R 1c to} R ^3c represent hydrogen atoms, and the rest represent (meth) acryloyl groups. ]

As the third compound, it is preferable ^{that R 1c} in the formula (3) represents a (meth) acryloyl group, and R ^2c and R ^3c represent a hydrogen atom (glycerin-1- (meth) acrylate). ^{It is more preferable that R 1c} in (3) represents an acryloyl group and R ^2c and R ^3c represent a hydrogen atom (glycerin-1-acrylate).

Further, the glycerin-1- (meth) acrylate is a compound (glycerin-2- (meth) acrylate) ^{in which R 2c} in the formula (3) represents a (meth) acryloyl group and R ^1c and R ^{3c represent a hydrogen atom.} May be a mixture of.

The content of the third compound is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 25 parts by mass or less, based on 100 parts by mass of the total of the first compound and the second compound. It is particularly preferably 20 parts by mass or less, and may be 0 parts by mass, preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, and particularly preferably 10 parts by mass or more. Is.

The content of the first compound is preferably 5% by mass or more, more preferably 20% by mass or more, still more preferably 40% by mass, based on 100% by mass of the total of the first compound, the second compound, and the third compound. % Or more, particularly preferably 50% by mass or more, and preferably 75% by mass or less, more preferably 73% by mass or less, still more preferably 70% by mass or less, and particularly preferably 68% by mass or less. ..

The content of the second compound is preferably 5% by mass or more, more preferably 9% by mass or more, still more preferably 12% by mass, based on 100% by mass of the total of the first compound, the second compound, and the third compound. % Or more, particularly preferably 17% by mass or more, and preferably 95% by mass or less, more preferably 77% by mass or less, still more preferably 57% by mass or less, and particularly preferably 45% by mass or less. ..

The content of the third compound may be 0% by mass, preferably 3% by mass or more, and more preferably 5% by mass or more, based on 100% by mass of the total of the first compound, the second compound, and the third compound. It is preferably 30% by mass or less, more preferably 18% by mass or less, and further preferably 15% by mass or less.

By adjusting the contents of the first compound, the second compound, and the third compound within the above range, the film thickness of the obtained cured film can be reduced.

The polymerizable compound (C) contains a polymerizable compound other than the first compound, the second compound, and the third compound (hereinafter, referred to as “other polymerizable compound”) as long as the effects of the present invention are not impaired. You may be.

Other polymerizable compounds include compounds that can be polymerized by active radicals and / or acids generated from the polymerization initiator (D), and compounds other than the above-mentioned first compound, second compound, and third compound. Just do it. For example, a compound having a polymerizable ethylenically unsaturated bond can be mentioned, and a (meth) acrylic acid ester compound is preferable.

Examples of other polymerizable compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and octyl (meth). Meta) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, phenoxyethyl (Meta) acrylate, nonylphenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, di Cyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl ( Meta) acrylate, phenyl (meth) acrylate, mono (2-acryloyloxyethyl) oxalate, N- [2- (acryloyloxy) ethyl] phthalimide, N- [2- (acryloyloxy) ethyl] tetrahydrophthalimide, 2- Monofunctional (meth) acrylate monomer such as (2-vinyloxyethoxy) ethyl (meth) acrylate;
1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) Acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclode Candimethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, Di (meth) acryloyloxy group in which two hydroxyl groups of polypropylene glycol di (meth) acrylate, neopentylglycol hydroxypivalic acid ester di (meth) acrylicate, and tris (2-hydroxyethyl) isocyanurate are substituted with (meth) acryloyloxy group. Di (meth) acrylate, bisphenol A, in which two hydroxyl groups of a diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of meta) acrylate or neopentyl glycol is substituted with a (meth) acryloyloxy group. Di (meth) acrylate in which two hydroxyl groups of the diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol are substituted with a (meth) acryloyloxy group, or 3 mol or more of ethylene oxide or 3 mol or more of ethylene oxide in 1 mol of trimethylolpropane. Di (meth) acrylate in which two hydroxyl groups of triol obtained by adding propylene oxide are substituted with (meth) acryloyloxy group, diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A A bifunctional (meth) acrylate monomer such as di (meth) acrylate in which the two hydroxyl groups of the above are substituted with a (meth) acryloyloxy group;
Trimethylol propantri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) Acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra ( Meta) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone Polyfunctional (meth) acrylate monomers such as modified dipentaerythritol hexa (meth) acrylate; and the like can be mentioned. Among them, a polyfunctional (meth) acrylate monomer having three or more polymerizable ethylenically unsaturated bonds is preferable, and a polyfunctional (meth) acrylate monomer having three to six polymerizable ethylenically unsaturated bonds is more preferable.

The total amount of the first compound, the second compound, and the third compound is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 85 in 100% by mass of the polymerizable compound (C). It is mass% or more, particularly preferably 95 mass% or more, and may be 100 mass% or more. In other words, the content of the other polymerizable compound is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 15% by mass or less, based on 100% by mass of the polymerizable compound (C). Particularly preferably, it is 5% by mass or less, and may be 0% by mass.

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 10 to 60% by mass, still more preferably, with respect to the total solid content of the colored curable resin composition. Is 10 to 55% by mass, particularly preferably 10 to 40% by mass. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming the coloring pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization by generating active radicals, acids, etc. by the action of light or heat, and a known polymerization initiator can be used. Examples of the polymerization initiator that generates an active radical include an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a biimidazole compound.

The O-acyloxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond.

Examples of the O-acyloxym compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6-] (2-Methylbenzoyl) -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,, 3-dimethyl-2,) 4-Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole] -3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropane- 1-on-2-imine can be mentioned. Commercially available products such as Irgacure OXE01, OXE02 (above, manufactured by BASF), N-1919, and NCI-730 (manufactured by ADEKA) may be used. Among them, the O-acyloxym compounds are N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1. At least one selected from the group consisting of −on-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, and NCI-730 is preferred. .. With these O-acyloxime compounds, a high-brightness color filter tends to be obtained.

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 and 2-dimethylamino-1- (4). -Morholinophenyl) -2-benzyl butane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one Can be mentioned. Commercially available products such as Irgacure 369, 907, 379 (all 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 and 2-hydroxy-2-methyl-1- [4- (2). -Hydroxyethoxy) phenyl] Propane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer, α, α-diethoxy Examples thereof 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).

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-). Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy) Styryl) -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- (fran-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 Can be mentioned.

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

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl)-. 4,4', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis (2-chlorophenyl) -4. , 4', 5,5'-tetraphenyl biimidazole, 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 (tri) Alkoxyphenyl) Biimidazole (see, for example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), the phenyl group at the 4,4', 5,5'-position is replaced with a carboalkoxy group. Examples thereof include biimidazole compounds (see, for example, Japanese Patent Application Laid-Open No. 7-10913).

Further, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthlenquinone, Kinone compounds such as 2-ethylanthraquinone and phenylquinone; examples thereof include 10-butyl-2-chloroacrydone, benzyl, methyl phenylglycoxylate, titanosen compounds and the like. These are preferably used in combination with a polymerization initiator such as amines.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethyl. Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyltosilates, Examples include benzointosilate.

As the polymerization initiator (D), a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound and a biimidazole compound is preferable, and an O-acyloxy compound is preferable. A polymerization initiator containing a compound compound is more preferable.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is a mass part. When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, so that the productivity of the color filter is improved.

<Solvent (E)>
The solvent (E) is not particularly limited, and a solvent usually used in the art can be used. For example, ester solvent (solvent containing -COO- in the molecule and not containing -O-), ether solvent (solvent containing -O- in the molecule and not containing -COO-), ether ester solvent (solvent in the molecule). Solvent containing -COO- and -O-), Ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (solvent containing OH in the molecule, -O-,- CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxides and the like.

Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, 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.

Examples of the ether solvent 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, and propylene glycol monoethyl ether. , Propropylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl Examples thereof include ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyletol and methyl anisol.

Examples of the ether ester solvent 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 Examples thereof include ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate.

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. And so on.

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

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

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

Among the above solvents, an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm is preferable from the viewpoint of coatability and drying property. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone And N, N-dimethylformamide are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and ethyl 3-ethoxypropionate are more preferable.

The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention. In other words, the total solid content of the colored curable resin composition is preferably 5 to 30% by mass, 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 the display characteristics tend to be good because the color density is not insufficient when the color filter is formed. ..

<Leveling agent (F)>
The colored curable resin composition of the present invention may further contain a leveling agent (F). Examples of the leveling agent (F) include a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, Examples thereof include KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan GK).

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

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include MegaFvck (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).

The content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, and more preferably 0.003% by mass or more and 0. It is 2% by mass or less, more preferably 0.005% by mass or more and 0.2% by mass or less. The content of the dispersant is not included in this content. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Thiol compound (G)>
The colored curable resin composition of the present invention may further contain a thiol compound (G). The thiol compound (G) is not particularly limited as long as it is a compound having at least one sulfanyl group in the molecule, but a compound having two or more sulfanyl groups in the molecule is preferable. Compounds having two or more sulfanil groups in the molecule include, for example, hexanedithiol, decandithiol, 1,4-bis (methylsulfanil) benzene, butanediol bis (3-sulfanil propionate), butanediol bis ( 3-Sulfanilacetate), ethylene glycol bis (3-sulfanilacetate), trimethylpropanthris (3-sulfanilacetate), butanediolbis (3-sulfanilpropionate), trimethylolpropanthris (3-sulfanilpropionate) ), Trimethylolpropanthris (3-sulfanilacetate), pentaerythritol tetrakis (3-sulfanilpropionate), pentaerythritol tetrakis (3-sulfanilacetate), trishydroxyethyltris (3-sulfanilpropionate), pentaerythritol Examples thereof include tetrakis (3-sulfanilbutyrate) and 1,4-bis (3-sulfanilbutyloxy) butane.

The content of the thiol compound (G) is preferably 0.1 to 5% by mass, more preferably 0.5 to 4% by mass, based on the total solid content of the colored curable resin composition. More preferably, it is 1 to 3% by mass. When the content of the thiol compound (G) is within the above range, a coloring pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

<Other ingredients>
The colored curable resin composition of the present invention may contain additives known in the art such as a polymerization initiator, a filler, other polymer compounds, an adhesion accelerator, and a light stabilizer, if necessary. good.

<Manufacturing method of colored curable resin composition>
Examples of the method for preparing the color-curable resin composition of the present invention include a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and necessary. It can be prepared by mixing the leveling agent (F), the thiol compound (G) and other components used according to the above.

When a pigment is used as the colorant (A), it is preferable to mix it with a part or all of the solvent (E) in advance. At this time, if necessary, a part or all of the pigment dispersant and the resin (B) may be blended. The desired color-curable resin composition can be prepared by mixing the remaining components with the pigment dispersion liquid thus obtained so as to have a predetermined concentration.

<Manufacturing method of color filter>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithography method, an inkjet method, a printing method and the like. Above all, the photolithography method is preferable. The photolithography method is a method in which the colored curable resin composition is applied to a substrate and dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. In the photolithography method, a colored coating film which is a cured film of the coloring composition layer can be formed by not using a photomask at the time of exposure and / or not developing. The colored pattern or colored coating film thus formed is the color filter of the present invention.

The film thickness of the color filter (cured film) to be produced is not particularly limited and can be appropriately adjusted according to the purpose, application, etc., for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, more preferably 0.1 to 20 μm. Is 0.5 to 6 μm. When the color filters have the same degree of color, a thinner film thickness is advantageous in manufacturing a display device that is lightweight, thin, and has high color reproducibility. From the viewpoint of thinning, the film thickness of the color filter (cured film) to be produced is preferably 3.00 μm or less, more preferably 2.50 μm or less, still more preferably 2.00 μm or less, and particularly preferably 1. It is 98 μm or less.

The substrate includes a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass whose surface is silica-coated, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, silicon, or on the substrate. Aluminum, silver, silver / copper / palladium alloy thin films, etc. are formed on the glass. Another color filter layer, resin layer, transistor, circuit, or the like may be formed on these substrates.

The formation of each color pixel by the photolithography method can be performed by a known or conventional device or condition. For example, it can be produced as follows.
First, a coloring curable resin composition is applied onto a substrate and dried under reduced pressure and / or by heating and drying (prebaking) to remove volatile components such as a solvent to obtain a smooth coloring composition layer.
Examples of the coating method include a spin coating method, a slit coating method, a slit and spin coating method, and the like.
When drying under reduced pressure, it is preferable to carry out drying under a pressure of 50 to 150 Pa in a temperature range of 20 to 25 ° C.
The temperature for heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.
The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected depending on the film thickness of the target color filter.

The colored composition layer is then exposed to form a colored coating. Further, when forming the coloring pattern, the coloring composition layer is exposed through a photomask. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
As the light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light less than 350 nm is cut by using a filter that cuts this wavelength range, and light near 436 nm, 408 nm, and 365 nm is selectively extracted by using a bandpass filter that extracts these wavelength ranges. You may do it. Specific examples thereof include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps and the like.
An exposure device such as a mask aligner and a stepper should be used because it is possible to uniformly irradiate the entire exposed surface with parallel rays and accurately align the photomask with the substrate on which the coloring composition layer is formed. Is preferable.

When forming the coloring pattern, the coloring pattern is formed on the substrate by bringing the exposed coloring composition layer into contact with a developing solution for development. By development, the unexposed portion of the coloring composition layer is dissolved in a developing solution and removed. As the developing solution, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of a paddle method, a dipping method, a spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.

Further, it is preferable to post-bake the obtained colored coating film or colored pattern. The post-bake temperature is preferably 80 to 250 ° C, more preferably 90 to 235 ° C. Further, the color curable resin composition of the present invention can produce a color filter having good performance even when the post-baking temperature is low. Therefore, the post-bake temperature may be 200 ° C. or lower, 150 ° C. or lower, or 130 ° C. or lower. Since the post-bake temperature is low, it is not necessary to consider damage to the substrate, elements, and the like, so that it can be suitably used for organic EL display devices, flexible displays, and the like. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

According to the color-curable resin composition of the present invention, the XYZ color system of CIE when the film thickness is 2.00 μm or less (preferably 1.98 μm or less) and the color is measured using a C light source. A green color filter (cured film) whose chromaticity coordinates in the range are in the range of x = 0.170 to 0.300 and y = 0.600 to 0.800;
The chromaticity coordinates in the XYZ color system of CIE when the film thickness is less than 2.00 μm (preferably 1.98 μm or less) and the color is measured using a C light source are x = 0.640 to 0. 710, a red color filter (cured film) in the range y = 0.290 to 0.330; and a film thickness of less than 2.00 μm (preferably 1.98 μm or less) and measured using a C light source. To prepare a blue color filter (cured film) in which the chromaticity coordinates in the XYZ color system of CIE when colored are in the range of x = 0.130 to 0.160 and y = 0.035 to 0.080. Can be done. Since the color filter is a dark color but a thin film, it is useful as a color filter used for a liquid crystal display device, an organic EL display device, an electronic paper, a solid-state imaging element, and the like, and among them, a flexible display (particularly an organic EL type). It is particularly useful as a color filter used in (flexible display).

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples as well as the present invention, and appropriate modifications are made to the extent that it can be adapted to the gist of the above and the following. Of course, it is possible to carry out, and all of them are included in the technical scope of the present invention. In the following, unless otherwise specified, "part" means "part by mass" and "%" means "% by mass".

[Synthesis of resin (B1)]
An appropriate amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, 350 parts of propylene glycol monomethyl ether acetate was placed therein, and the mixture was heated to 85 ° C. with stirring. Then 70 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] A mixed solution of 202 parts of a mixture of decan-9-ylacrylate (content ratio is 1: 1 in molar ratio), 78 parts of vinyl toluene (isomer mixture), and 100 parts of propylene glycol monomethyl ether acetate is added dropwise over 4 hours. bottom. On the other hand, a solution prepared by dissolving 33 parts of the polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 167 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of dropping the initiator solution, the mixture was held at 85 ° C. for 4 hours, cooled to room temperature, and measured with a B-type viscometer (23 ° C.), which had a viscosity of 431 mPas and a solid content of 38.1% (resin B1). ) A solution was obtained. The weight average molecular weight Mw of the resulting copolymer 1.04 × 10 ^4, the degree of dispersion 2.03, acid value on solid basis was 139mg-KOH / g. Resin B1 has the following structural units.

[Synthesis of resin (B2)]
An appropriate amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, 362 parts of propylene glycol monomethyl ether acetate was placed therein, and the mixture was heated to 80 ° C. with stirring. Then 58 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] A mixed solution of 167 parts of a mixture of decane-9-ylacrylate (content ratio 1: 1 in molar ratio), 65 parts of 2-ethylhexyl acrylate, and 111 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a solution prepared by dissolving 27 parts of the polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 210 parts of propylene glycol monomethyl ether acetate was added dropwise over 5.5 hours. After completion of dropping the initiator solution, the mixture was held at 80 ° C. for 4 hours and then cooled to room temperature to obtain a copolymer (resin B2) solution having a B-type viscosity (23 ° C.) of 43 mPas and a solid content of 29.8%. .. The weight average molecular weight Mw of the resulting copolymer 1.09 × 10 ^4, the degree of dispersion 2.25, acid value on solid basis was 148mg-KOH / g. Resin B2 has the following structural units.

[Preparation of colorant dispersion (A1)]
C. I. Pigment Green 59 10 parts Acrylic pigment dispersant 1.4 parts Acrylic pigment dispersion resin Resin (B1) 4.6 parts propylene glycol monomethyl ether acetate 55 parts Mix the above components and sufficiently disperse the pigment using a bead mill. As a result, a dispersion liquid (A1) was obtained.

[Preparation of colorant dispersion (A2)]
C. I. Pigment Yellow 150 10 parts Acrylic pigment dispersant 4.5 parts Acrylic pigment dispersion resin Resin (B2) 3.5 parts propylene glycol monomethyl ether acetate 66 parts Mix the above components and sufficiently disperse the pigment using a bead mill. As a result, a dispersion liquid (A2) was obtained.

[Preparation of colorant dispersion (A3)]
C. I. Pigment Yellow 138 10 parts Acrylic pigment dispersant 3.2 parts Acrylic pigment dispersion resin resin (B2) 4.2 parts propylene glycol monomethyl ether acetate 66 parts Mix the above components and sufficiently disperse the pigment using a bead mill. As a result, a dispersion liquid (A3) was obtained.

[Preparation of colorant dispersion (A4)]
C. I. Pigment Red 269 10 parts Acrylic pigment dispersant 2.5 parts Acrylic pigment dispersion resin (B3) 3.0 parts Propylene glycol monomethyl ether acetate 56 parts Mix the above components and disperse the pigment sufficiently using a bead mill. Obtained a dispersion liquid (A4).

[Preparation of colorant dispersion (A5)]
C. I. Pigment Yellow 139 10 parts Acrylic pigment dispersant 3.5 parts Acrylic pigment dispersion resin (B3) 2.5 parts Propylene glycol monomethyl ether acetate 67 parts Mix the above components and disperse the pigment sufficiently using a bead mill. Obtained a dispersion liquid (A5).

[Preparation of colorant dispersion (A6)]
C. I. Pigment Violet 19 10 parts Acrylic pigment dispersant 2.8 parts Acrylic pigment dispersion resin (B3) 3.3 parts Propylene glycol monomethyl ether acetate 61 parts Mix the above components and sufficiently disperse the pigment using a bead mill. Obtained a dispersion liquid (A6).

[Preparation of colorant dispersion (A7)]
C. I. Pigment Blue 15: 6 10 parts Acrylic pigment dispersant 2.5 parts Acrylic pigment dispersion resin (B3) 2.5 parts Propylene glycol monomethyl ether acetate 68 parts Mix the above components and sufficiently disperse the pigment using a bead mill. The dispersion liquid (A7) was obtained.

[Preparation of colorant dispersion (A8)]
Compound represented by formula (X) (manufactured by Taiyo Fine Chemical Co., Ltd.) 10 parts Acrylic pigment dispersant 4.0 parts Acrylic pigment dispersion resin (B3) 4.0 parts Propylene glycol monomethyl ether acetate 107 parts Mix the above components and mix. A dispersion liquid (A8) was obtained by sufficiently dispersing the pigment using a bead mill.

[Examples 1 to 11, Comparative Examples 1 to 5]
[Preparation of Color Curable Resin Composition]
A colorant dispersion, a resin, a polymerizable compound, a polymerization initiator, a leveling agent, a thiol compound, and a solvent were mixed so as to have the compositions shown in Table 1, and each color-curable resin composition was obtained.

In Table 1, each component is as follows.
-Colorant (A1): C.I. I. Pigment Green 59
-Colorant (A2): C.I. I. Pigment Yellow 150
-Colorant (A3): C.I. I. Pigment Yellow 138
-Colorant (A4): C.I. I. Pigment Red 269
-Colorant (A5): C.I. I. Pigment Yellow 139
-Colorant (A6): C.I. I. Pigment Violet 19
-Colorant (A7): C.I. I. Pigment Blue 15: 6
-Colorant (A8): Compound represented by formula (X) -Resin (B1): Resin B1 (in terms of solid content)
-Resin (B2): Resin B2 (solid content conversion)
-Resin (B3): Acrylic pigment dispersion resin (B3)
Polymerizable compound (C1): Aronix (registered trademark) M-930 (manufactured by Toagosei Co., Ltd .; glycerin-1,3-diacrylate 9%, glycerin triacrylate 91%)
Polymerizable compound (C2): Aronix (registered trademark) M-920 (manufactured by Toagosei Co., Ltd .; glycerin-1,3-diacrylate 60%, glycerin triacrylate 33%, glycerin-1-acrylate 7%)
Polymerizable compound (C3): A mixture of glycerin monoacrylate, glycerin diacrylate and glycerin triacrylate (manufactured by Toa Synthetic Co., Ltd .; glycerin-1,3-diacrylate 64%, glycerin triacrylate 22%, glycerin-1-acrylate) 14%)
Polymerizable compound (C4): ethylene oxide glycerin triacrylate (EO9 mol) (A-GLY-9E; manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
Polymerizable compound (C5): Dipentaerythritol polyacrylate (A-9550; manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
Polymerizable compound (C6): Trimethylolpropane triacrylate (A-TMPT; manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
Polymerizable compound (C7): pentaerythritol tri and tetraacrylate (A-TMM-3LM-N; manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
Polymerizable compound (C8): Dipentaerythritol ethoxylated polyacrylate (A-DPH-12E; manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
-Polymerization initiator (D1): NCI-730 (manufactured by ADEKA Corporation; O-acyloxime compound)
-Solvent (E1): Propylene glycol monomethyl ether acetate-Leveling agent (F1): Fluorine-containing group / lipophilic group-containing oligomer (Megafuck (registered trademark) F554; manufactured by DIC Corporation)
Thiol compound (G1): trimethylolpropane tris (3-sulfanyl propionate) (TMMP-20P; manufactured by SC Organic Chemistry Co., Ltd.)

[Preparation of colored coating film]
The obtained colored curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Inc.) by a spin coating method, and then dried under reduced pressure under a pressure of 100 Pa. Then, it was prebaked at 70 ° C. for 2 minutes to form a colored composition layer. After allowing to cool, the colored composition layer was irradiated with light at an exposure amount of ^{60 mJ / cm 2} (based on 365 nm) in an atmospheric atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). Then, it was post-baked in an oven at 100 ° C. for 30 minutes to obtain a colored coating film.

[Measurement of film thickness]
The film thickness of the obtained colored coating film was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 2.

[Saturation evaluation]
The obtained colored coating film was spectrally measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity in the XYZ color system of CIE was measured using the characteristic function of the C light source. The coordinates (x, y) and Y were measured. The results are shown in Table 2.

Claims (9)

Contains a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E).
A colored curable resin composition in which the polymerizable compound (C) contains a first compound represented by the formula (1) and a second compound represented by the formula (2).

[In formula (1), ^{any one of R 1a to} R ^3a represents a hydrogen atom, and the rest independently represent a (meth) acryloyl group. ]

[In formula (2), R ^{1b to} R ^3b each independently represent a (meth) acryloyl group. ] The colored curable resin composition according to claim 1, wherein the mass ratio of the first compound to the second compound (first compound / second compound) is 5/95 to 93/7. The polymerizable compound (C) may further have a third compound represented by the formula (3).
The content of the first compound is 5 to 75% by mass, the content of the second compound is 5 to 95% by mass, and the content of the first compound is 5 to 95% by mass in the total of 100% by mass of the first compound, the second compound, and the third compound. The colored curable resin composition according to claim 1 or 2, wherein the content of the three compounds is 0 to 20% by mass.

[In formula (3), ^{any two of R 1c to} R ^3c represent hydrogen atoms, and the rest represent (meth) acryloyl groups. ] The chromaticity coordinates in the XYZ color system of CIE when the film thickness is 2.00 μm or less and the color is measured using the C light source are x = 0.170 to 0.300, y = 0.600 to The colored curable resin composition according to any one of claims 1 to 3, which can form a cured film in the range of 0.800. The chromaticity coordinates in the XYZ color system of CIE when the film thickness is less than 2.00 μm and the color is measured using the C light source are x = 0.640 to 0.710 and y = 0.290 to. The colored curable resin composition according to any one of claims 1 to 3, which can form a cured film in the range of 0.330. The chromaticity coordinates in the XYZ color system of CIE when the film thickness is less than 2.00 μm and the color is measured using the C light source are x = 0.130 to 0.160 and y = 0.035 to The colored curable resin composition according to any one of claims 1 to 3, which can form a cured film in the range of 0.080. A color filter formed from the color curable resin composition according to any one of claims 1 to 6. An organic EL display device including the color filter according to claim 7. A flexible display including the color filter according to claim 7.