Colored curable resin composition

Abstract

The present invention aims to provide a color curable resin composition capable of forming a color filter having a dark color and a thin film. The color curable resin composition comprises a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), wherein the polymerizable compound (C) comprises a first compound represented by formula (1) and a second compound represented by formula (2). [In formula (1), R 1a ~R 3a Any one of them represents a hydrogen atom, and the rest independently represent a (meth)acryloyl group. [In formula (2), R 1b ~R 3b Each independently represents a (meth)acryloyl group.]

Description

Technical Field

[0001] The present invention relates to a colored curable resin composition, a color filter formed from the colored curable resin composition, and a display device including the color filter. Background Art

[0002] Color filters used in display devices such as liquid crystal display devices, electroluminescent display devices, and plasma displays, or solid-state imaging devices such as CCD and CMOS sensors are produced from colored curable resin compositions.

[0003] Conventionally, known polymerizable compounds used in colored curable resin compositions include oxirane-modified glycerol triacrylate (see, for example, Patent Document 1) and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (see, for example, Patent Document 2).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2008-164886

[0007] Patent Document 2: Japanese Patent Application Laid-Open No. 2019-112494 Summary of the Invention

[0008] However, in recent years, the demand for display devices and solid-state imaging devices with a wide color gamut and good color reproducibility has continued to increase, and there is a growing demand for dark, thin-film color filters. However, with conventional colored curable resin compositions, there is still room for research on thin-film production in the production of dark color filters. Therefore, the present invention is to provide a colored curable resin composition capable of forming dark, thin-film color filters.

[0009] The gist of the present invention is as follows.

[0010] [1] A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E),

[0011] The polymerizable compound (C) includes a first compound represented by formula (1) and a second compound represented by formula (2).

[0012]

[0013] [In formula (1), R 1a ~R 3a Any one of them represents a hydrogen atom, and the rest each independently represents a (meth)acryloyl group.]

[0014]

[0015] [In formula (2), R 1b ~R 3b Each independently represents a (meth)acryloyl group.]

[0016] [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.

[0017] [3] The colored curable resin composition according to [1] or [2], wherein the polymerizable compound (C) may further include a third compound represented by formula (3),

[0018] In 100% by mass of the total of the first compound, the second compound, and the third compound, 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 third compound is 0 to 20% by mass.

[0019]

[0020] [In formula (3), R 1c ~R 3c Any two of them represent hydrogen atoms, and the remaining represents a (meth)acryloyl group.]

[0021] [4] The colored curable resin composition according to any one of [1] to [3], which can form a cured film having a film thickness of 2.00 μm or less and a chromaticity coordinate of the CIE XYZ colorimetric system within the range of x=0.170 to 0.300 and y=0.600 to 0.800 when colorimetrically measured using a C light source.

[0022] [5] The colored curable resin composition according to any one of [1] to [3], which can form a cured film having a film thickness of less than 2.00 μm and a chromaticity coordinate in the range of x = 0.640 to 0.710 and y = 0.290 to 0.330 in the CIE XYZ colorimetric system when colorimetry is performed using a C light source.

[0023] [6] The colored curable resin composition according to any one of [1] to [3], which can form a cured film having a film thickness of less than 2.00 μm and a chromaticity coordinate of the CIE XYZ colorimetric system within the range of x=0.130 to 0.160 and y=0.035 to 0.080 when colorimetrically measured using a C light source.

[0024] [7] A color filter formed from the colored curable resin composition according to any one of [1] to [6].

[0025] [8] An organic EL display device comprising the color filter described in [7].

[0026] [9] A flexible display comprising the color filter described in [7].

[0027] According to the colored curable resin composition of the present invention, a color filter having a deep color and a thin film can be provided. DETAILED DESCRIPTION

[0028] <Colored curable resin composition>

[0029] The colored curable resin composition of the present invention is characterized by comprising a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), wherein the polymerizable compound (C) comprises a first compound represented by formula (1) (hereinafter sometimes referred to as glycerol di(meth)acrylate) and a second compound represented by formula (2) (hereinafter sometimes referred to as glycerol tri(meth)acrylate).

[0030] In this specification, "(meth)acrylate" refers to at least one selected from acrylate and methacrylate. "(meth)acrylic acid" and "(meth)acryloyl" have the same meaning. Furthermore, unless otherwise specified, compounds listed as components in this specification may be used alone or in combination.

[0031] Colorant (A)

[0032] The colorant (A) may be any of a dye and a pigment, but preferably contains a pigment. As the pigment, known pigments can be used, and examples thereof include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

[0033] Specifically, yellow pigments such as CI 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, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, and 214 can be mentioned;

[0034] CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments;

[0035] 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, 266, 268, 269, 273 and other red pigments;

[0036] CI Pigment Blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments;

[0037] CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments;

[0038] Green pigments of CI Pigment Green 7, 36, 58, and 59;

[0039] Brown pigments such as CI Pigment Brown 23 and 25;

[0040] Black pigments such as CI Pigment Black 1 and 7, etc.

[0041] In addition, as the pigment, a compound represented by formula (x) can be used.

[0042]

[0043] When forming a red pixel, it is preferred to use a combination of CI Pigment Red 254 and CI Pigment Red 177; a combination of CI Pigment Red 254, CI Pigment Red 177 and CI Pigment Yellow 150; a combination of CI Pigment Red 254, CI Pigment Red 242 and CI Pigment Yellow 150; a combination of CI Pigment Red 254 and CI Pigment Orange 38; a combination of CI Pigment Red 254, CI Pigment Red 177 and CI Pigment Yellow 138; a combination of CI Pigment Red 254, CI Pigment Red 177 and CI Pigment Yellow 139; a combination of CI Pigment Red 269, CI Pigment Yellow 139, CI Pigment Violet 19, etc.

[0044] When forming a green pixel, it is preferred to use a combination of CI Pigment Green 59, CI Pigment Yellow 138 and CI Pigment Yellow 150; a combination of CI Pigment Green 59, CI Pigment Yellow 139 and CI Pigment Yellow 185; a combination of CI Pigment Green 58, CI Pigment Yellow 138 and CI Pigment Yellow 150; a combination of CI Pigment Green 58 and CI Pigment Yellow 150; a combination of CI Pigment Green 58 and CI Pigment Yellow 138; a combination of CI Pigment Green 59 and CI Pigment Yellow 150; a combination of CI Pigment Green 59 and CI Pigment Yellow 138; a combination of CI Pigment Green 59, CI Pigment Green 58 and CI Pigment Yellow 138; a combination of CI Pigment Green 59, CI Pigment Green 58 and CI Pigment Yellow 150; a combination of CI Pigment Green 59, CI Pigment Green 58, CI Pigment Yellow 150 and CI Pigment Yellow 138, etc.

[0045] When forming a blue pixel, it is preferable to use a combination of CI Pigment Blue 15:6 and Compound (x); a combination of CI Pigment Blue 15:6 and CI Pigment Violet 23, or the like.

[0046] The pigment may be subjected to rosin treatment, surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, grafting treatment on the pigment surface using a polymer compound, micronization treatment using a sulfuric acid micronization method, or washing treatment using an organic solvent, water, or the like for removing impurities, or removal treatment of ionic impurities using an ion exchange method, etc., as needed.

[0047] The pigment preferably has a uniform particle size. In addition, by containing a pigment dispersant and performing a dispersion treatment, a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained.

[0048] Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. Examples of the pigment dispersant include, by trade name, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOWLEN (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Lubrizol), EFKA (manufactured by CIBA), AJISPER (manufactured by Ajinomoto Fine Chemicals Co., Ltd.), and Disperbyk (manufactured by BYK-Chemie).

[0049] When a pigment dispersant is used, its usage amount is preferably 1% to 100% by mass, more preferably 5% to 50% by mass, relative to the total amount of the pigment. When the usage amount of the pigment dispersant is within the above range, a uniformly dispersed pigment dispersion tends to be obtained.

[0050] 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, particularly preferably 95% by mass or more, and may be 100% by mass.

[0051] Coloring agent (A) can contain dye.As dye, is not particularly limited, can use known dye, can enumerate solvent dye, acid dye, direct dye, mordant dye etc.As dye, for example, can enumerate the known dye of recording in the compound with the material of hue except pigment, dyeing guide (color dyeing company) that is classified in color index (TheSocietyofDyersandColouristspublishes).In addition, according to chemical structure, can enumerate azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes etc.Wherein, preferred organic solvent soluble dyes.

[0052] Specifically, CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189,

[0053] CI Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247,

[0054] CI Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86,

[0055] CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60,

[0056] CI Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139,

[0057] CI solvent dyes such as CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35;

[0058] CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 156 7, 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,

[0059] CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182 , 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, ​​383, 388, 394, 401, 412, 417, 418, 422, 426,

[0060] CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173,

[0061] CI Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102,

[0062] CI Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123 , 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340,

[0063] CI acid green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109 and other CI acid dyes;

[0064] CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141,

[0065] CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250,

[0066] CI Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107,

[0067] CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104,

[0068] CI Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167 7, 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,

[0069] CI direct dyes such as CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;

[0070] CI Disperse Yellow 51, 54, 76,

[0071] CI Disperse Violet 26, 27,

[0072] CI disperse dyes such as CI Disperse Blue 1, 14, 56, 60;

[0073] CI Basic Red 1, 10,

[0074] CI Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89,

[0075] CI Basic Violet 2;

[0076] CI Basic Red 9;

[0077] CI basic dyes such as CI Basic Green 1;

[0078] CI Reactive Yellow 2, 76, 116,

[0079] CI Reactive Orange 16,

[0080] CI reactive dyes such as CI Reactive Red 36;

[0081] CI Medium Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65,

[0082] CI Medium Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95,

[0083] CI Medium Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48,

[0084] CI Medium 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,

[0085] CI Medium 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,

[0086] CI mordant dyes such as CI Mordant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53;

[0087] CI vat dyes such as CI Vat Green 1, etc.

[0088] 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 may be 0% by mass.

[0089] The content of the colorant (A) is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and even more preferably 10 to 50% by mass relative to the total solid content of the colored curable resin composition. When the content of the colorant (A) is within this range, the color density of the resulting color filter is sufficient, and the composition can contain the required amounts of the resin (B) and the polymerizable compound (C), thereby forming a pattern with sufficient mechanical strength.

[0090] In this specification, the term "total solids content" refers to the amount obtained by subtracting the solvent content from the total amount of the colored curable resin composition. The total solids content and the content of each component relative to the total solids content can be measured using known analytical methods such as liquid chromatography or gas chromatography.

[0091] Resin (B)

[0092] 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].

[0093] Resin [K1]: A copolymer comprising structural units derived from at least one type (a) selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as "(a)"), and structural units derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)");

[0094] Resin [K2]: a copolymer having a structural unit derived from (a), a structural unit derived from (b), and a structural unit derived from a monomer (c) copolymerizable with (a) (which is different from (a) and (b)) (hereinafter sometimes referred to as "(c)");

[0095] Resin [K3]: a copolymer having a structural unit derived from (a) and a structural unit derived from (c);

[0096] Resin [K4]: a copolymer having a structural unit derived from (a) to which a structural unit derived from (b) and a structural unit derived from (c) are added;

[0097] Resin [K5]: a copolymer in which a structural unit derived from (b) is added with a structural unit derived from (a) and a structural unit derived from (c);

[0098] Resin [K6]: A copolymer having a structural unit derived from (b) to which (a) is added, a structural unit further to which a carboxylic acid anhydride is added, and a structural unit derived from (c).

[0099] Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;

[0100] Unsaturated dicarboxylic acids such as 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, dimethyltetrahydrophthalic acid, and 1,4-cyclohexenedicarboxylic acid;

[0101] Bicyclic unsaturated compounds containing a carboxyl group, such as 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]hept-2-ene, and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;

[0102] Unsaturated dicarboxylic anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride;

[0103] Unsaturated mono(meth)acryloyloxyalkyl) esters of polycarboxylic acids having a valence of 2 or more, such as mono(2-(meth)acryloyloxyethyl)succinate and mono(2-(meth)acryloyloxyethyl)phthalate;

[0104] Unsaturated acrylic acid esters containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid.

[0105] Among them, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferred from the viewpoint of copolymerization reactivity and solubility of the resulting resin in an aqueous alkaline solution.

[0106] (b) refers to a polymerizable compound having, for example, a cyclic ether structure having 2 to 4 carbon atoms (e.g., at least one selected from an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) Preferably, the monomer has a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0107] As (b), for example, there can be mentioned a monomer (b1) having an oxetane group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "(b1)"), a monomer (b2) having an oxetane group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "(b2)"), and a monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "(b3)").

[0108] Examples of (b1) include a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)") and a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-2)").

[0109] Examples of (b1-1) include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyl)acrylate, 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(glycidyloxymethyl)styrene, etc.

[0110] Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer (registered trademark) M100; manufactured by Daicel Corporation), compounds represented by formula (I), and compounds represented by formula (II).

[0111]

[0112] [In formula (I) and formula (II), R a and R b It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group.

[0113] X a and X b Indicates a single bond, *-R c -, *-R c -O-, *-R c -S- or *-R c -NH-.

[0114] R c It represents an alkanediyl group having 1 to 6 carbon atoms.

[0115] *Indicates the bonding site with O.]

[0116] Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group and the like.

[0117] Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxy group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, and 4-hydroxybutyl.

[0118] As R a and R b , preferably, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are mentioned, and more preferably, a hydrogen atom and a methyl group are mentioned.

[0119] Examples of the alkanediyl group include 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-1,6-diyl group.

[0120] As X a and X b , preferably, a single bond, a methylene group, an ethylene group, *-CH2-O-, and *-CH2CH2-O- are mentioned, and more preferably, a single bond and *-CH2CH2-O- (* represents a bonding site with O) are mentioned.

[0121] Examples of the compound represented by formula (I) include compounds represented by any one of formulas (I-1) to (I-15). Among them, compounds represented by formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), or formulas (I-11) to (I-15) are preferred, and compounds represented by formula (I-1), formula (I-7), formula (I-9), or formula (I-15) are more preferred.

[0122]

[0123] Examples of the compound represented by formula (II) include compounds represented by any one of formulas (II-1) to (II-15). Among them, compounds represented by formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), or formulas (II-11) to (II-15) are preferred, and compounds represented by formula (II-1), formula (II-7), formula (II-9), or formula (II-15) are more preferred.

[0124]

[0125] The compound represented by formula (I) and the compound represented by formula (II) may be used alone or in combination of two or more. When the compound represented by formula (I) and the compound represented by formula (II) are used in combination, the ratio of their content [compound represented by formula (I):compound represented by formula (II)] is preferably 5:95 to 95:5, more preferably 20:80 to 80:20, on a molar basis.

[0126] As (b2), a monomer having an oxetane group and a (meth)acryloyloxy group is more preferred. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, and 3-ethyl-3-acryloyloxyethyloxetane.

[0127] As (b3), a monomer having a tetrahydrofuranyl group and a (meth)acryloyloxy group is more preferred. Specific examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

[0128] As (b), (b1) is preferred in terms of improving the reliability of the obtained color filter in terms of heat resistance, chemical resistance, etc. Furthermore, (b1-2) is more preferred in terms of excellent storage stability of the colored curable resin composition.

[0129] Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0](meth)acrylate. 2,6 ] decane-8-yl ester (in this technical field, it is commonly known as "dicyclopentyl (meth)acrylate". In addition, it is sometimes called "tricyclodecyl (meth)acrylate"), tricyclo[5.2.1.0 2,6 (Meth)acrylates such as decen-8-yl acrylate (commonly known in the art as "dicyclopentenyl (meth)acrylate"), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

[0130] (Meth)acrylates containing a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

[0131] dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;

[0132] 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-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene Bicyclic unsaturated compounds such as cyclo[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, and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene;

[0133] Dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide;

[0134] 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, etc.

[0135] Among them, 2-hydroxyethyl (meth)acrylate, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, 2-ethylhexyl (meth)acrylate, and the like are preferred from the viewpoint of copolymerization reactivity and heat resistance.

[0136] In the resin [K1], the ratio of the structural units derived from each unit is preferably 2 to 60 mol% of the structural units derived from (a) and 40 to 98 mol% of the structural units derived from (b) in all the structural units constituting the resin [K1]. More preferably, the structural units derived from (a) are 10 to 50 mol% and the structural units derived from (b) are 50 to 90 mol%.

[0137] When the ratio of the structural unit of the resin [K1] is within the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the obtained color filter tend to be excellent.

[0138] Resin [K1] can be produced, for example, by referring to the method described in the document "Experimental Methods for Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd., Chemical Dojin, 1st edition, 1st printing, published on March 1, 1972) and the cited documents described in the document.

[0139] Specifically, the following method can be used: a predetermined amount of (a) and (b), a polymerization initiator, and a solvent are placed in a reaction vessel, and a deoxygenated atmosphere is created, for example, by replacing oxygen with nitrogen, and the mixture is heated and kept warm while stirring. It should be noted that the polymerization initiator and solvent used here are not particularly limited, and polymerization initiators and solvents commonly used in this field can be used. For example, as polymerization initiators, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) can be used. As solvents, any solvent that dissolves each monomer can be used, and the solvents described later as the solvent (E) of the colored curable resin composition of the present invention can be used.

[0140] The resulting copolymer may be used directly as a post-reaction solution, after concentration or dilution, or in a solid (powder) form by reprecipitation or other methods. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during the polymerization, the post-reaction solution can be used directly to prepare the colored curable resin composition of the present invention, thereby simplifying the production process of the colored curable resin composition of the present invention.

[0141] In the resin [K2], the ratio of the structural units derived from each unit is preferably 2 to 45 mol% of the structural units derived from (a), 2 to 95 mol% of the structural units derived from (b), and 1 to 65 mol% of the structural units derived from (c) in all the structural units constituting the resin [K2]. More preferably, the structural units derived from (a) are 5 to 40 mol%, the structural units derived from (b) are 5 to 80 mol%, and the structural units derived from (c) are 5 to 60 mol%.

[0142] When the ratio of the structural units of the resin [K2] is within the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance, heat resistance, and mechanical strength of the obtained color filter tend to be excellent.

[0143] The resin [K2] can be produced, for example, in the same manner as described as the method for producing the resin [K1].

[0144] In the resin [K3], the ratio of the structural units derived from each unit is preferably 2 to 60 mol% of the structural units derived from (a) and 40 to 98 mol% of the structural units derived from (c) in all the structural units constituting the resin [K3]. More preferably, the structural units derived from (a) are 10 to 50 mol% and the structural units derived from (c) are 50 to 90 mol%.

[0145] The resin [K3] can be produced, for example, in the same manner as described as the method for producing the resin [K1].

[0146] Resin [K4] can be produced by obtaining a copolymer of (a) and (c), and then adding a cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and / or carboxylic anhydride contained in (a).

[0147] First, a copolymer of (a) and (c) is produced in the same manner as described as the method for producing resin [K1]. In this case, the ratio of the structural units derived from each unit is preferably the same as the ratio exemplified for resin [K3].

[0148] Next, the cyclic ether having 2 to 4 carbon atoms contained in (b) is reacted with a portion of the carboxylic acid and / or carboxylic anhydride derived from (a) in the above copolymer.

[0149] After the copolymer of (a) and (c) is produced, the atmosphere in the flask is replaced from nitrogen to air, and (b), a reaction catalyst for a carboxylic acid or carboxylic anhydride and a cyclic ether (e.g., tris(dimethylaminomethyl)phenol, etc.), and a polymerization inhibitor (e.g., hydroquinone, etc.) are placed in the flask and reacted at, for example, 60 to 130° C. for 1 to 10 hours to produce resin [K4].

[0150] The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, relative to 100 mol of (a). Within this range, there is a tendency for the storage stability of the colored curable resin composition, the developability during pattern formation, and the balance between the solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern to be improved. Since cyclic ethers have high reactivity and are less likely to leave unreacted (b), (b1) is preferred as the (b) used in resin [K4], and (b1-1) is more preferred.

[0151] The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass relative 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 relative to 100 parts by mass of the total amount of (a), (b) and (c).

[0152] The reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the calorific value based on the polymerization, etc. In addition, the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the calorific value based on the polymerization, etc., similarly to the polymerization conditions.

[0153] As a first step, the resin [K5] is subjected to the same method as for producing the resin [K1] to obtain a copolymer of (b) and (c). Similarly to the above, the obtained copolymer may be used as is after the reaction, after concentration or dilution, or after being obtained as a solid (powder) by reprecipitation or the like.

[0154] The ratio of the structural units derived from (b) and (c) relative to the total molar number of all structural units constituting the above-mentioned copolymer is preferably 5 to 95 mol% for the structural units derived from (b) and 5 to 95 mol% for the structural units derived from (c), and more preferably 10 to 90 mol% for the structural units derived from (b) and 10 to 90 mol% for the structural units derived from (c).

[0155] Furthermore, resin [K5] is obtained by reacting the carboxylic acid or carboxylic anhydride contained in (a) with the cyclic ether derived from (b) contained in the copolymer of (b) and (c) under the same conditions as in the method for producing resin [K4].

[0156] The amount of (a) reacted with the copolymer is preferably 5 to 80 mol per 100 mol of (b). Since cyclic ethers have high reactivity and are less likely to leave unreacted (b), (b1) is preferred as (b) for use in the resin [K5], and (b1-1) is more preferred.

[0157] Resin [K6] is a resin obtained by further reacting carboxylic acid anhydride with resin [K5]. Carboxylic acid anhydride is reacted with hydroxyl groups generated by the reaction of cyclic ether and carboxylic acid or carboxylic acid anhydride.

[0158] Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride. The amount of the carboxylic anhydride used is preferably 0.5 to 1 mol relative to 1 mol of (a).

[0159] Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] decyl ester / (meth) acrylic acid copolymer resins [K1]; (meth) acrylate glycidyl ester / (meth) acrylate benzyl ester / (meth) acrylic acid copolymer, (meth) acrylate glycidyl ester / styrene / (meth) acrylic acid copolymer, acrylic acid 3,4-epoxy tricyclic [5.2.1.0 2,6 ]Decyl ester / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] decyl ester / (meth) acrylic acid / N-cyclohexyl maleimide / (meth) acrylate 2-hydroxyethyl ester copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ]Decyl ester / (meth)acrylic acid / vinyl toluene copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6] decyl ester / (meth)acrylic acid / 2-ethylhexyl (meth)acrylate copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane / (meth)acrylic acid / styrene copolymer and other resins [K2]; benzyl (meth)acrylate / (meth)acrylic acid copolymer, styrene / (meth)acrylic acid copolymer and other resins [K3]; benzyl (meth)acrylate / (meth)acrylic acid copolymer with glycidyl (meth)acrylate added thereto, tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymer with glycidyl (meth)acrylate added thereto, tricyclodecyl (meth)acrylate / (meth)acrylic acid copolymer with glycidyl (meth)acrylate added thereto, Resins such as a resin obtained by adding glycidyl (meth)acrylate to a benzyl (meth)acrylate / (meth)acrylic acid copolymer [K4]; a resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate, a resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / styrene / glycidyl (meth)acrylate, etc. [K5]; a resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / styrene / glycidyl (meth)acrylate, and further reacting tetrahydrophthalic anhydride with the resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate [K6], etc.

[0160] Among them, the resin (B) is preferably the resin [K1] and the resin [K2], and particularly preferably the resin [K2].

[0161] 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 this range, the hardness of the color filter is improved, the residual film rate is high, the solubility of the unexposed portion in the developer is good, and the resolution of the colored pattern tends to be improved.

[0162] The dispersion degree [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1-6, more preferably 1.2-4.

[0163] The acid value of 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, calculated on a solids basis. The acid value is measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin (B) and can be determined, for example, by titration with an aqueous potassium hydroxide solution.

[0164] The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and even more preferably 17 to 55% by mass relative to the total solid content. When the content of the resin (B) is within this range, a colored pattern can be formed, and the resolution and residual film rate of the colored pattern tend to be improved.

[0165] <Polymerizable compound (C)>

[0166] The polymerizable compound (C) contains the first compound (glycerol di(meth)acrylate) represented by formula (1).

[0167]

[0168] [In formula (1), R 1a ~R 3a Any one of them represents a hydrogen atom, and the rest each independently represents a (meth)acryloyl group.]

[0169] As the first compound, R in formula (1) is preferably 2a Represents a hydrogen atom, R 1a and R 3a The compound (glycerol-1,3-di(meth)acrylate) each independently represents a (meth)acryloyl group, and more preferably R in formula (1) 2a Represents a hydrogen atom, R 1a and R 3a This represents a compound containing an acryloyl group (glycerol-1,3-diacrylate).

[0170] In addition, glycerol-1,3-di(meth)acrylate may also be 3a Represents a hydrogen atom, R 1a and R 2a Each independently represents a mixture of a (meth)acryloyl compound (glycerol-1,2-di(meth)acrylate).

[0171] The polymerizable compound (C) contains a second compound (glycerol tri(meth)acrylate) represented by formula (2) in addition to the above-mentioned first compound.

[0172]

[0173] [In formula (2), R 1b ~R 3b Each independently represents a (meth)acryloyl group.]

[0174] As the second compound, R 1b ~R 3b This represents an acryloyl compound (glycerol triacrylate).

[0175] The mass ratio of the first compound to the second compound (the first compound / the second compound) is preferably 5 / 95 to 93 / 7, more preferably 20 / 80 to 90 / 10, further preferably 40 / 60 to 85 / 15, and particularly preferably 50 / 50 to 80 / 20. In other words, in 100% by mass of the total of the first compound and the second compound, the content of the first compound is preferably 5% to 93% by mass, more preferably 20% to 90% by mass, further preferably 40% to 85% by mass, and particularly preferably 50% to 80% by mass. In addition, the content of the second compound is preferably 7% to 95% by mass, more preferably 10% to 80% by mass, further preferably 15% to 60% by mass, and particularly preferably 20% to 50% by mass. By adjusting the mass ratio of the first compound to the second compound to the above range, the thickness of the cured film obtained can be made thinner.

[0176] The polymerizable compound (C) may further contain a third compound represented by formula (3) (hereinafter sometimes referred to as glycerol mono(meth)acrylate) in addition to the first compound and the second compound.

[0177]

[0178] [In formula (3), R 1c ~R 3c Any two of them represent hydrogen atoms, and the remaining represents a (meth)acryloyl group.]

[0179] As the third compound, R in formula (3) is preferably 1c represents a (meth)acryloyl group, R 2c and R 3c The compound (glycerol-1-(meth)acrylate) representing a hydrogen atom is more preferably R in formula (3) 1c Represents acryloyl, R 2c and R 3c A compound representing a hydrogen atom (glycerol-1-acrylate).

[0180] In addition, glycerol-1-(meth)acrylate may also be 2c represents a (meth)acryloyl group, R 1c and R 3c A mixture of compounds expressing hydrogen atoms (glycerol-2-(meth)acrylate).

[0181] The content of the third compound relative to 100 parts by mass of the total of the first compound and the second compound is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, further preferably 25 parts by mass or less, particularly preferably 20 parts by mass or less, and may also be 0 parts by mass. It is preferably 1 part by mass or more, more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, and particularly preferably 10 parts by mass or more.

[0182] The content of the first compound is preferably 5% by mass or more, more preferably 20% by mass or more, further preferably 40% by mass or more, and particularly preferably 50% by mass or more in 100% by mass of the total of the first compound, the second compound, and the third compound. In addition, it is preferably 75% by mass or less, more preferably 73% by mass or less, further preferably 70% by mass or less, and particularly preferably 68% by mass or less.

[0183] The content of the second compound in 100 mass% of the total of the first compound, the second compound and the third compound is preferably 5 mass% or more, more preferably 9 mass% or more, further preferably 12 mass% or more, and particularly preferably 17 mass%. In addition, it is preferably 95 mass% or less, more preferably 77 mass% or less, further preferably 57 mass% or less, and particularly preferably 45 mass% or less.

[0184] The content of the third compound in 100% by mass of the total of the first compound, the second compound and the third compound can be 0% by mass, preferably 3% by mass or more, more preferably 5% by mass or more, and is preferably 30% by mass or less, more preferably 18% by mass or less, and further preferably 15% by mass or less.

[0185] By adjusting the contents of the first compound, the second compound, and the third compound to fall within the above-mentioned ranges, the thickness of the resulting cured film can be reduced.

[0186] The polymerizable compound (C) may contain polymerizable compounds other than the first compound, the second compound, and the third compound (hereinafter referred to as "other polymerizable compounds") unless the effects of the present invention are impaired.

[0187] The other polymerizable compound may be any compound other than the first, second, and third compounds as long as it is polymerizable by active radicals and / or acids generated by the polymerization initiator (D). For example, compounds having a polymerizable ethylenically unsaturated bond are mentioned, preferably (meth)acrylate compounds.

[0188] Examples of other polymerizable compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, cyclohexyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, nonylphenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and (meth)acrylate. Monofunctional (meth)acrylate monomers such as diethylaminoethyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, N-[2-(acryloyloxy)ethyl]phthalimide, N-[2-(acryloyloxy)ethyl]tetrahydrophthalimide, and 2-(2-vinyloxyethoxy)ethyl (meth)acrylate;

[0189] 1,3-Butanediol 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, tricyclodecane dimethanol 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, polypropylene glycol di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate, the two hydroxyl groups of which are ( Bifunctional (meth)acrylate monomers such as di(meth)acrylates substituted with (meth)acryloyloxy groups, di(meth)acrylates obtained by adding 4 or more ethylene oxide or propylene oxide to 1 mol of neopentyl glycol and replacing two hydroxyl groups of the diol with (meth)acryloyloxy groups, di(meth)acrylates obtained by adding 2 or more ethylene oxide or propylene oxide to 1 mol of bisphenol A and replacing two hydroxyl groups of the diol with (meth)acryloyloxy groups, di(meth)acrylates obtained by adding 3 or more ethylene oxide or propylene oxide to 1 mol of trimethylolpropane and replacing two hydroxyl groups of the triol with (meth)acryloyloxy groups, and di(meth)acrylates obtained by adding 4 or more ethylene oxide or propylene oxide to 1 mol of bisphenol A and replacing two hydroxyl groups of the diol with (meth)acryloyloxy groups;

[0190] Polyfunctional (meth)acrylate monomers such as trimethylolpropane tri(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(meth)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, and caprolactone-modified dipentaerythritol hexa(meth)acrylate may be used. Among them, a polyfunctional (meth)acrylate monomer having three or more polymerizable ethylenically unsaturated bonds is preferred, and a polyfunctional (meth)acrylate monomer having 3 to 6 polymerizable ethylenically unsaturated bonds is more preferred.

[0191] 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, even more preferably 85% by mass or more, particularly preferably 95% by mass or more, in 100% by mass of the polymerizable compound (C), and may be 100% by mass. In other words, the content of the other polymerizable compounds is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 15% by mass or less, particularly preferably 5% by mass or less, in 100% by mass of the polymerizable compound (C), and may be 0% by mass.

[0192] The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 10 to 60% by mass, further preferably 10 to 55% by mass, and particularly preferably 10 to 40% by mass relative to the total solid content of the colored curable resin composition. When the content of the polymerizable compound (C) is within this range, the residual film rate during formation of a colored pattern and the chemical resistance of the color filter tend to improve.

[0193] <Polymerization initiator (D)>

[0194] The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating active free radicals, acids, etc. under the action of light or heat to initiate polymerization, and known polymerization initiators can be used. Examples of polymerization initiators that generate active free radicals include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds.

[0195] The O-acyl oxime compound is a compound having a partial structure represented by formula (d1).

[0196]

[0197] Examples of the O-acyl oxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, 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-carbazol-3-yl]ethane-1-imine, and N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine. 1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolanylmethoxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, and N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine. Commercially available products such as Irgacure OXE01 and OXE02 (all manufactured by BASF), N-1919, and NCI-730 (manufactured by ADEKA) can also be used. Among these, the O-acyl oxime compound is preferably at least one selected from N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, and NCI-730. These O-acyl oxime compounds tend to produce color filters with high brightness.

[0198] The alkylphenone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). In these partial structures, the benzene ring may have a substituent.

[0199]

[0200] Examples of compounds having a partial structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane-1-one. Commercially available products such as Irgacure 369, 907, and 379 (all manufactured by BASF) can also be used.

[0201] Examples of the compound having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, and benzyl dimethyl ketal.

[0202] In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (d2).

[0203] Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine. [2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine.

[0204] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) can be used.

[0205] Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Application Laid-Open Nos. 6-75372 and 6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, ) biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, see Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), and biimidazole compounds in which the phenyl group at the 4,4',5,5'-position is substituted with a carboalkoxy group (for example, see Japanese Patent Application Laid-Open No. 7-10913, etc.).

[0206] Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl benzoylformate, and titanocene compounds. These are preferably used in combination with a polymerization initiator aid such as an amine.

[0207] Examples of the acid generator include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium hexafluoroantimonate; nitrobenzyl toluenesulfonates; and benzoin toluenesulfonates.

[0208] The polymerization initiator (D) preferably contains at least one selected from alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and biimidazole compounds, and more preferably contains an O-acyloxime compound.

[0209] The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, there is a tendency for increased sensitivity to shorten the exposure time, thereby improving the productivity of the color filter.

[0210] Solvent (E)

[0211] The solvent (E) is not particularly limited, and solvents commonly used in this field can be used. Examples include ester solvents (solvents containing -COO- and not -O- in the molecule), ether solvents (solvents containing -O- and not -COO- in the molecule), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and not -COO- in the molecule), alcohol solvents (solvents containing OH and not -O-, -CO-, and -COO- in the molecule), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

[0212] Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0213] 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, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dimethoxy-1-butanol, 3-methoxy-3-methylbutanol ... Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether and methyl anisole, etc.

[0214] 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, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0215] Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0216] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0217] Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

[0218] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0219] Among the above-mentioned solvents, organic solvents having a boiling point of 120°C to 180°C at 1 atm are preferred from the perspectives of coating and drying properties. Preferred solvents include 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, with propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and ethyl 3-ethoxypropionate being more preferred.

[0220] The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, relative to 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 this range, the flatness during coating is improved, and when a color filter is formed, the color density is not insufficient, thereby tending to improve display characteristics.

[0221] <Leveling agent (F)>

[0222] The colored curable resin composition of the present invention may further contain a leveling agent (F). Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms. These may have polymerizable groups in their side chains.

[0223] Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specific examples include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (trade names: manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.).

[0224] Examples of the fluorine-based surfactant include surfactants having a fluorine carbon chain in the molecule. Specific examples include FLUORAD (registered trademark) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemicals Laboratories, Ltd.), etc.

[0225] Examples of the fluorine-containing silicone surfactant include surfactants having a siloxane bond and a fluorocarbon chain in the molecule, and more specifically, MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, and MEGAFAC F443 (manufactured by DIC Corporation).

[0226] The content of the leveling agent (F) is preferably 0.001% to 0.2% by mass, more preferably 0.003% to 0.2% by mass, and even more preferably 0.005% to 0.2% by mass relative to the total amount of the colored curable resin composition. This content does not include the content of the dispersant described above. When the content of the leveling agent (F) is within this range, the flatness of the color filter can be improved.

[0227] <Thiol compound (G)>

[0228] 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 has at least one sulfanyl group in the molecule, but is preferably a compound having two or more sulfanyl groups in the molecule. Examples of the compound having two or more sulfanyl groups in the molecule include hexanedithiol, decanedithiol, 1,4-bis(methylsulfanyl)benzene, butanediol bis(3-sulfanylpropionate), butanediol bis(3-sulfanyl acetate), ethylene glycol bis(3-sulfanyl acetate), trimethylolpropane tris(3-sulfanyl acetate), butanediol bis(3-sulfanylpropionate), trimethylolpropane tris(3-sulfanylpropionate), trimethylolpropane tris(3-sulfanyl acetate), pentaerythritol tetrakis(3-sulfanylpropionate), pentaerythritol tetrakis(3-sulfanyl acetate), trishydroxyethyl tris(3-sulfanylpropionate), pentaerythritol tetrakis(3-sulfanylbutyrate), and 1,4-bis(3-sulfanylbutoxy)butane.

[0229] The content of the thiol compound (G) is preferably 0.1 to 5% by mass, more preferably 0.5 to 4% by mass, and even more preferably 1 to 3% by mass relative to the total solid content of the colored curable resin composition. When the content of the thiol compound (G) is within the above range, a colored pattern can be formed with higher sensitivity, and there is a tendency for the productivity of the color filter to improve.

[0230] <Other ingredients>

[0231] The colored curable resin composition of the present invention may contain additives known in the art, such as a polymerization initiation aid, a filler, other polymer compounds, an adhesion promoter, and a light stabilizer, as needed.

[0232] <Method for producing a colored curable resin composition>

[0233] As a method for preparing the colored curable resin composition of the present invention, for example, it can be prepared by mixing the colorant (A), the resin (B), the polymerizable compound (C), the polymerization initiator (D), the solvent (E), and, if necessary, the leveling agent (F), the thiol compound (G), and other components.

[0234] When a pigment is used as the colorant (A), it is preferably premixed with part or all of the solvent (E). In this case, the pigment dispersant and part or all of the resin (B) may be added as needed. The desired colored curable resin composition can be prepared by mixing the remaining components into the thus obtained pigment dispersion to achieve a desired concentration.

[0235] <Color filter manufacturing method>

[0236] As a method for producing a colored pattern from the colored curable resin composition of the present invention, photolithography, inkjet method, printing method, etc. can be cited. Among them, photolithography is preferred. Photolithography is a method in which the above-mentioned colored curable resin composition is applied to a substrate and dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithography method, a colored coating film as a cured film of the above-mentioned colored composition layer can be formed without using a photomask and / or developing during exposure. The colored pattern and colored coating film thus formed are the color filter of the present invention.

[0237] The film thickness of the color filter (cured film) produced is not particularly limited and can be appropriately adjusted according to the purpose, use, etc., for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm. It should be noted that when the color filter has the same chromaticity, the thinner the film thickness, the more advantageous it is when manufacturing a lightweight, thin display device with high color reproducibility. From the viewpoint of thin filmization, the film thickness of the color filter (cured film) produced is preferably 3.00 μm or less, more preferably 2.50 μm or less, further preferably 2.00 μm or less, and particularly preferably 1.98 μm or less.

[0238] As the substrate, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda-lime glass coated with silicon dioxide, resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, silicon, and substrates having thin films of aluminum, silver, or silver / copper / palladium alloys formed thereon can be used. Other color filter layers, resin layers, transistors, circuits, and the like can be formed on these substrates.

[0239] The formation of each color pixel by photolithography can be performed using known or customary equipment and conditions. For example, the formation can be performed as follows.

[0240] First, a colored curable resin composition is applied onto a substrate, and volatile components such as a solvent are removed by drying under reduced pressure and / or heating (pre-baking) to obtain a smooth colored composition layer.

[0241] Examples of the coating method include spin coating, slit coating, and slit spin coating.

[0242] When drying under reduced pressure is performed, it is preferably performed at a pressure of 50 to 150 Pa and a temperature range of 20 to 25°C.

[0243] The temperature during 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.

[0244] The film thickness of the colored composition layer is not particularly limited and may be appropriately selected depending on the film thickness of the target color filter.

[0245] Next, the colored composition layer is exposed to form a colored coating film. In addition, when forming a colored pattern, the colored composition layer is exposed through a photomask. The pattern on the photomask is not particularly limited, and a pattern corresponding to the intended use is used.

[0246] The light source used for exposure is preferably one that generates light with a wavelength of 250 to 450 nm. For example, a filter that cuts off wavelengths less than 350 nm can be used to block light, or bandpass filters that selectively filter out light near 436 nm, 408 nm, or 365 nm can be used to selectively filter out light in these wavelength ranges. Specific examples include mercury lamps, light-emitting diodes, metal halide lamps, and halogen lamps.

[0247] In order to uniformly irradiate the entire exposure surface with parallel light and accurately align the photomask and the substrate on which the colored composition layer is formed, it is preferable to use an exposure device such as a mask aligner and a stepper.

[0248] When forming a colored pattern, the exposed colored composition layer is brought into contact with a developer and developed to form a colored pattern on the substrate. The unexposed portions of the colored composition layer are dissolved in the developer and removed by development. Preferred developers include aqueous solutions of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide. 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. The developer may also contain a surfactant.

[0249] The development method may be any of a spin immersion method, a dipping method, a spray method, etc. Furthermore, the substrate may be tilted at any angle during development.

[0250] After development, water washing is preferably performed.

[0251] In addition, it is preferred 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. In addition, the colored curable resin composition of the present invention can produce a color filter with good performance even when the post-bake temperature is low. Therefore, the post-bake temperature can be 200°C or less, or 150°C or less, or 130°C or less. By making the post-bake temperature low, there is no need to consider damage to the substrate, components, etc., and therefore it can be preferably used in organic EL display devices, flexible displays, etc. The post-bake time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

[0252] According to the colored curable resin composition of the present invention, the following color filters can be produced: in particular, a green color filter (cured film) having a film thickness of 2.00 μm or less (preferably 1.98 μm or less) and a chromaticity coordinate of the CIE XYZ colorimetric system in the range of x = 0.170 to 0.300 and y = 0.600 to 0.800 when colorimetrically measured using a C light source; and a green color filter (cured film) having a film thickness of less than 2.00 μm (preferably 1.98 μm or less) and a chromaticity coordinate of less than 2.00 μm (preferably 1.98 μm or less) when colorimetrically measured using a C light source. A red color filter (cured film) having chromaticity coordinates of the CIE XYZ colorimetric system in the range of x = 0.640 to 0.710 and y = 0.290 to 0.330 when measuring color; and a blue color filter (cured film) having a film thickness of less than 2.00 μm (preferably 1.98 μm or less) and having chromaticity coordinates of the CIE XYZ colorimetric system in the range of x = 0.130 to 0.160 and y = 0.035 to 0.080 when measuring color using a C light source. Since this color filter has a dark color and is a thin film, it is useful as a color filter for use in liquid crystal displays, organic EL displays, electronic paper, solid-state imaging devices, and the like. It is particularly useful as a color filter for use in flexible displays (particularly organic EL flexible displays).

[0253] Example

[0254] The present invention will be described in more detail below with reference to the following examples. However, the present invention is not limited to the following examples and can be implemented by adding appropriate modifications within the scope of the aforementioned and subsequent descriptions. Such modifications are all within the technical scope of the present invention. It should be noted that, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass."

[0255] [Synthesis of Resin (B1)]

[0256] A suitable amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen. 350 parts of propylene glycol monomethyl ether acetate was added and heated to 85°C while stirring. Subsequently, 70 parts of acrylic acid and 3,4-epoxytricyclo[5.2.1.0 2,6 ]Decan-8-yl ester and 3,4-epoxytricyclic acrylate [5.2.1.0 2 ,6 ] A mixed solution of 202 parts of a mixture of decane-9-yl ester (containing a ratio of 1:1 by molar ratio), 78 parts of vinyltoluene (isomer mixture), and 100 parts of propylene glycol monomethyl ether acetate. On the other hand, a solution obtained by dissolving 33 parts of a polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) in 167 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After the addition of the initiator solution was completed, the mixture was kept at 85°C for 4 hours and then cooled to room temperature to obtain a copolymer (resin B1) solution having a viscosity of 431 mPas and a solid content of 38.1% as measured by a B-type viscometer (23°C). The weight-average molecular weight Mw of the resulting copolymer was 1.04×10 4 The dispersion degree was 2.03, and the acid value based on solid content was 139 mg-KOH / g. Resin B1 had the following structural units.

[0257]

[0258] [Synthesis of Resin (B2)]

[0259] A suitable amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen. 362 parts of propylene glycol monomethyl ether acetate was added and heated to 80°C while stirring. Subsequently, 58 parts of acrylic acid and 3,4-epoxytricyclo[5.2.1.0 2,6 ]Decan-8-yl ester and 3,4-epoxytricyclic acrylate [5.2.1.0 2 ,6 ] A mixed solution of 167 parts of a mixture of 9-decane esters (containing a ratio of 1:1 by molar ratio), 65 parts of 2-ethylhexyl acrylate, and 111 parts of propylene glycol monomethyl ether acetate. On the other hand, a solution obtained by dissolving 27 parts of a 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 the addition of the initiator solution was completed, the mixture was kept at 80°C for 4 hours and then cooled to room temperature to obtain a copolymer (resin B2) solution with a B-type viscosity (23°C) of 43 mPas and a solid content of 29.8%. The weight-average molecular weight Mw of the generated copolymer was 1.09×10 4The dispersion degree was 2.25, and the acid value based on solid content was 148 mg-KOH / g. Resin B2 had the following structural units.

[0260]

[0261] [Preparation of Colorant Dispersion (A1)]

[0262]

[0263] The above components are mixed, and the pigment is sufficiently dispersed using a bead mill to obtain a dispersion (A1).

[0264] [Preparation of Colorant Dispersion (A2)]

[0265]

[0266] The above components are mixed, and the pigment is sufficiently dispersed using a bead mill to obtain a dispersion (A2).

[0267] [Preparation of Colorant Dispersion (A3)]

[0268]

[0269] The above components are mixed, and the pigment is sufficiently dispersed using a bead mill to obtain a dispersion (A3).

[0270] [Preparation of Colorant Dispersion (A4)]

[0271]

[0272] The above components were mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a dispersion (A4).

[0273] [Preparation of Colorant Dispersion (A5)]

[0274]

[0275] The above components were mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a dispersion (A5).

[0276] [Preparation of Colorant Dispersion (A6)]

[0277]

[0278]

[0279] The above components were mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a dispersion (A6).

[0280] [Preparation of Colorant Dispersion (A7)]

[0281]

[0282] The above components were mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a dispersion (A7).

[0283] [Preparation of Colorant Dispersion (A8)]

[0284]

[0285] The above components were mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a dispersion (A8).

[0286]

[0287] [Examples 1 to 11, Comparative Examples 1 to 5]

[0288] [Preparation of Colored Curable Resin Composition]

[0289] The colorant dispersion, resin, polymerizable compound, polymerization initiator, leveling agent, thiol compound, and solvent were mixed to form the composition shown in Table 1, thereby obtaining each colored curable resin composition.

[0290] [Table 1]

[0291]

[0292] In Table 1, the components are as follows.

[0293] Colorant (A1): CI Pigment Green 59

[0294] Colorant (A2): CI Pigment Yellow 150

[0295] Colorant (A3): CI Pigment Yellow 138

[0296] Colorant (A4): CI Pigment Red 269

[0297] Colorant (A5): CI Pigment Yellow 139

[0298] Colorant (A6): CI Pigment Violet 19

[0299] Colorant (A7): CI Pigment Blue 15:6

[0300] Colorant (A8): a compound represented by formula (X)

[0301] Resin (B1): Resin B1 (solid content conversion)

[0302] Resin (B2): Resin B2 (solid content conversion)

[0303] Resin (B3): Acrylic pigment dispersion resin (B3)

[0304] Polymerizable compound (C1): ARONIX (registered trademark) M-930 (manufactured by Toagosei Co., Ltd.; glycerol-1,3-diacrylate 9%, glycerol triacrylate 91%)

[0305] Polymerizable compound (C2): ARONIX (registered trademark) M-920 (manufactured by Toagosei Co., Ltd.; glycerol-1,3-diacrylate 60%, glycerol triacrylate 33%, glycerol-1-acrylate 7%)

[0306] Polymerizable compound (C3): A mixture of glycerol monoacrylate, glycerol diacrylate, and glycerol triacrylate (manufactured by Toagosei Co., Ltd.; glycerol-1,3-diacrylate 64%, glycerol triacrylate 22%, glycerol-1-acrylate 14%)

[0307] Polymerizable compound (C4): ethylene oxide-containing glyceryl triacrylate (EO 9 mol) (A-GLY-9E; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0308] Polymerizable compound (C5): dipentaerythritol polyacrylate (A-9550; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0309] Polymerizable compound (C6): trimethylolpropane triacrylate (A-TMPT; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0310] Polymerizable compound (C7): Pentaerythritol tri- and tetraacrylate (A-TMM-3LM-N; manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0311] Polymerizable compound (C8): Ethoxylated dipentaerythritol polyacrylate (A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0312] Polymerization initiator (D1): NCI-730 (manufactured by ADEKA Corporation; O-acyl oxime compound)

[0313] Solvent (E1): Propylene glycol monomethyl ether acetate

[0314] Leveling agent (F1): an oligomer containing a fluorine-containing group and a lipophilic group (MEGAFAC (registered trademark) F554; manufactured by DIC Corporation)

[0315] Thiol compound (G1): trimethylolpropane tris(3-sulfanylpropionate) (TMMP-20P; manufactured by SC Organic Chemical Co., Ltd.)

[0316] [Production of color coating film]

[0317] The obtained colored curable resin composition was applied to a 5 cm square glass substrate (EAGLE2000; manufactured by CORNING) by spin coating and then dried under reduced pressure at 100 Pa. It was then pre-baked at 70°C for 2 minutes to form a colored composition layer. After cooling, the composition was exposed to light at 60 mJ / cm in an air atmosphere using an exposure machine (TME-150RSK; manufactured by TOPCON). 2 The colored composition layer was irradiated with light at an exposure dose of 100 nm (based on 365 nm). Thereafter, post-baking was performed in an oven at 100° C. for 30 minutes to obtain a colored coating film.

[0318] [Measurement of film thickness]

[0319] 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.).

[0320] [Chroma Evaluation]

[0321] The spectrum of the obtained colored coating film was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity coordinates (x, y) and Y in the CIE XYZ color system were measured using the characteristic function of illuminant C. The results are shown in Table 2.

[0322] [Table 2]

[0323]

Claims

1. A color filter formed from a colored curable resin composition, wherein the color filter has a dark color and a film thickness of less than 2.00 μm, wherein the colored curable resin composition comprises a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E). The polymerizable compound (C) comprises a first compound represented by formula (1) and a second compound represented by formula (2), The mass ratio of the first compound to the second compound, i.e., the first compound / the second compound, is 5 / 95 to 90 / 10. In formula (1), R 1a ~R 3a Any one of them represents a hydrogen atom, and the rest each independently represents a (meth)acryloyl group, In formula (2), R 1b ~R 3b Each independently represents a (meth)acryloyl group.

2. The color filter according to claim 1, wherein The polymerizable compound (C) may further have a third compound represented by formula (3), In 100% by mass of the total of the first compound, the second compound, and the third compound, 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 third compound is 0 to 20% by mass. In formula (3), R 1c ~R 3c Any two of them represent hydrogen atoms, and the remaining represents a (meth)acryloyl group.

3. The color filter according to claim 1 or 2, wherein The colored curable resin composition can form a cured film having a film thickness of 2.00 μm or less and having chromaticity coordinates in the range of x=0.170 to 0.300 and y=0.600 to 0.800 in the CIE XYZ colorimetric system when colorimetry is performed using a C light source.

4. The color filter according to claim 1 or 2, wherein The colored curable resin composition can form a cured film having a thickness of less than 2.00 μm and a chromaticity coordinate in the range of x=0.640 to 0.710 and y=0.290 to 0.330 in the CIE XYZ colorimetric system when colorimetrically measured using a C light source.

5. The color filter according to claim 1 or 2, wherein The colored curable resin composition can form a cured film having a thickness of less than 2.00 μm and a chromaticity coordinate in the range of x=0.130 to 0.160 and y=0.035 to 0.080 in the CIE XYZ colorimetric system when colorimetrically measured using a C light source. 6 . An organic EL display device comprising the color filter according to claim 1 . 7 . A flexible display comprising the color filter according to claim 1 .

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