Colored curable resin composition, color filter, display device, and solid state imaging device

Abstract

To provide a colored curable resin composition capable of giving a cured product excellent in a residual film rate before and after image development, and pattern formation property.SOLUTION: A colored curable resin composition includes: a coloring agent; a resin; a polymerizable compound; a polyfunctional thiol compound; and a photoinitiator. The polymerizable compound is a compound having a methacryloyl group. The content of the polyfunctional thiol compound is more than 10 mass% on the basis of a total amount of a solid content of the colored curable resin composition.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a colored curable resin composition, a color filter, a display device, and a solid-state imaging device. [Background technology]

[0002] Color filters used in color liquid crystal displays, color imaging devices (solid-state imaging devices), etc. are produced from a cured product of a coloring composition (colored curable resin composition). As such a composition, a composition containing a colorant, a resin (binder resin), etc. is known (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2019-086555 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, cured products of conventional compositions tend to have a large change in film thickness before and after development, a low residual film rate, and also tend to be insufficient in terms of pattern formability, so there is still room for improvement.

[0005] Therefore, a main object of the present invention is to provide a colored curable resin composition that can give a cured product that is excellent in the remaining film rate before and after development and in the pattern formability. [Means for solving the problem]

[0006] The present invention provides a colored curable resin composition according to [1] and [2], a color filter according to [3], a display device according to [4], and a solid-state imaging device according to [5]. [1] A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polyfunctional thiol compound, and a photopolymerization initiator, the polymerizable compound is a compound having a methacryloyl group, The content of the polyfunctional thiol compound is more than 10 mass% based on the total amount of solids of the colored curable resin composition. Colored curable resin composition. [2] The polymerizable compound is a compound having two or more methacryloyl groups. The colored curable resin composition according to [1]. [3] A color filter formed from the colored curable resin composition according to [1] or [2]. [4] A display device comprising the color filter according to [3]. [5] A solid-state imaging device comprising the color filter according to [3]. Effect of the Invention

[0007] According to the present invention, there is provided a colored curable resin composition capable of giving a cured product having excellent film remaining rate and pattern formability before and after development. According to the present invention, there is also provided a color filter formed from such a colored curable resin composition. Furthermore, according to the present invention, there is also provided a display device or a solid-state imaging device including the color filter. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Hereinafter, embodiments of the present invention will be described in detail, however, the present invention is not limited to the following embodiments.

[0009] In this specification, a numerical range indicated using "~" indicates a range including the numerical values ​​before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this specification, the upper limit or lower limit value described in one numerical range may be replaced with the upper limit or lower limit value of another numerical range described in stages. In addition, in the numerical ranges described in this specification, the upper limit or lower limit value of the numerical range may be replaced with a value shown in the examples.

[0010] In this specification, (meth)acrylate means acrylate or the corresponding methacrylate, and the same applies to other similar expressions such as (meth)acrylic acid, (meth)acryloyl, (meth)acrylic acid esters, etc.

[0011] In this specification, unless otherwise specified, the materials exemplified below may be used alone or in combination of two or more within the range of the conditions. When multiple substances corresponding to each component exist, the content of each component means the total amount of the multiple substances unless otherwise specified.

[0012] [Colored curable resin composition] The colored curable resin composition of the present embodiment contains a colorant (hereinafter, sometimes referred to as "colorant (A)"), a resin (hereinafter, sometimes referred to as "resin (B)"), a polymerizable compound (hereinafter, sometimes referred to as "polymerizable compound (C)"), a polyfunctional thiol compound (hereinafter, sometimes referred to as "polyfunctional thiol compound (D)"), and a photopolymerization initiator (hereinafter, sometimes referred to as "photopolymerization initiator (E)"). The colored curable resin composition of the present embodiment may contain a solvent (hereinafter, sometimes referred to as "solvent (F)"), a leveling agent (hereinafter, sometimes referred to as "leveling agent (G)"), a coupling agent (hereinafter, sometimes referred to as "coupling agent (H)"), and other components.

[0013] <Colorant (A)> Examples of the colorant (A) include dyes and pigments. These dyes and pigments may be used alone or in combination of two or more.

[0014] The dye is not particularly limited, and known dyes can be used. Examples of the dye include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of the dye include compounds classified as having a hue other than pigments in the Color Index (published by The Society of Dyers and Colourists), and known dyes described in Dyeing Notes (Shikisensha). In addition, according to the chemical structure, examples of the dye include azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, phthalocyanine dyes, perylene dyes, quinophthalone dyes, and isoindoline dyes. Of these, the dye is preferably an organic solvent-soluble dye.

[0015] Specifically, the dyes have the following Color Index (CI) numbers: CI Solvent Yellow 4 (hereinafter, CI Solvent Yellow will be omitted and only the number will be listed. Other similar expressions may also be listed only by the number.), 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 117, 162, 163, 167, 189; CI Solvent Red 24, 45, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; CI Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 77, 86, 99; CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI Solvent Blue 4, 5, 14, 18, 35, 36, 37, 38, 44, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35; CI solvent dyes, etc. 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, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 1 82, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, ​​383, 388, 394, 401, 412, 417, 418, 422, 426; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173; CI Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102; CI Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 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, 249, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340; CI Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109; CI acid dyes such as CI Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141; CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; CI Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 87, 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, 16 6, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82; CI direct dyes, etc. CI Disperse Yellow 51, 54, 76; CI Disperse Violet 26, 27; CI Disperse Blue 1, 14, 56, 60; CI disperse dyes such as CI Basic Red 1, 10; CI Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89; CI Basic Violet 2; CI Basic Red 9; CI Basic Green 1; CI Basic Dyes, etc. CI Reactive Yellow 2, 76, 116; CI Reactive Orange 16; CI Reactive Red 36; CI reactive dyes, etc. CI Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI Mordant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95; CI Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI Mordant Violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58; CI Mordant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84; CI Mordant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53; CI mordant dyes, etc. CI Bat Green 1; CI vat dyes etc.

[0016] Known pigments can be used as the pigment. Examples of the pigment include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists). In addition, according to the chemical structure, azo pigments, cyanine pigments, triphenylmethane pigments, xanthene pigments, anthraquinone pigments, naphthoquinone pigments, quinoneimine pigments, methine pigments, azomethine pigments, squarylium pigments, acridine pigments, styryl pigments, coumarin pigments, quinoline pigments, nitro pigments, phthalocyanine pigments, perylene pigments, quinophthalone pigments, and isoindoline pigments can be mentioned. Examples of such pigments include the following pigments.

[0017] Green pigments: CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, etc. Yellow pigments: 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, 214, 231, 233, etc. Orange pigments: CI Pigment Orange 13, 31, 34, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, etc. Red pigments: CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 178, 179, 180, 190, 192, 202, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 272, 273, 291, etc. Blue pigments: CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, etc. Purple pigments: CI Pigment Violet 1, 19, 23, 29, 32, 36, 38, etc. Brown pigment: CI Pigment Brown 23, 25, etc. Black pigment: CI Pigment Black 1, 7, 31, 32, etc.

[0018] With regard to these pigments, one kind of pigment or a plurality of pigments may be used for each color, and pigments of each color may be combined.

[0019] The colorant (A) is preferably one or more pigments, more preferably two or more pigments, even more preferably two or more pigments selected from the group consisting of a green pigment, a yellow pigment, a blue pigment, a purple pigment, and a red pigment, particularly preferably a combination of a green pigment and a yellow pigment, a combination of a green pigment, a yellow pigment, and a blue pigment, a blue pigment and a purple pigment, a red pigment and a yellow pigment, or a combination of a red pigment, a yellow pigment, a green pigment, and a blue pigment, and most preferably a combination of a green pigment and a yellow pigment.

[0020] Among green pigments, a phthalocyanine pigment is preferable, more preferably at least one selected from the group consisting of a halogenated copper phthalocyanine pigment, a halogenated zinc phthalocyanine pigment, and a halogenated aluminum phthalocyanine pigment, and further preferably CI Pigment Green 7, 36, 58, 59, 62, or 63.

[0021] Among the yellow pigments, at least one selected from the group consisting of quinophthalone yellow pigments, metal-containing yellow pigments, and isoindoline yellow pigments is preferred, CI Pigment Yellow 129, 138, 139, 150, or 185 is more preferred, and CI Pigment Yellow 138, 139, 150, or 185 is even more preferred.

[0022] The pigment may be subjected to, as necessary, a rosin treatment; a surface treatment using a pigment derivative having an acidic or basic group introduced therein; a grafting treatment to the pigment surface using a polymeric compound; a micronization treatment using a sulfuric acid micronization method; a washing treatment using an organic solvent, water, or the like to remove impurities; a removal treatment using an ion exchange method for ionic impurities, or the like. The particle size of the pigment is preferably approximately uniform. The pigment can be made into a pigment dispersion liquid in which the pigment is uniformly dispersed in the pigment dispersant solution by adding a pigment dispersant and performing a dispersion treatment. The pigments may be dispersed individually or in a mixture of multiple types.

[0023] Examples of pigment dispersants include silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric, polyester-based, polyamine-based, and acrylic surfactants. Examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, and polyethyleneimines. Examples of commercially available surfactants include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOWRENE (manufactured by Kyoeisha Chemical Co., Ltd.), Solpers (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF Japan Ltd.), AJISPER (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), and Disperbyk (manufactured by BYK-Chemie).

[0024] When a pigment dispersant is used, the amount used is preferably 10 to 200 parts by mass, more preferably 15 to 180 parts by mass, and even more preferably 20 to 160 parts by mass, relative to 100 parts by mass of the pigment. When the amount of the pigment dispersant used is within the above range, a pigment dispersion in a more uniformly dispersed state tends to be obtained when two or more pigments are used.

[0025] The total content of the colorant (A) is 0.1% by mass or more based on the total amount of solids in the colored curable resin composition. The content of the colorant (A) is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, particularly preferably 5% by mass or more, most preferably 10% by mass or more, and preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less based on the total amount of solids in the colored curable resin composition. When the content of the colorant (A) is within the above range, it tends to be easier to obtain the desired spectrum and color density. In this specification, the "total amount of solids in the colored curable resin composition" means the total amount of components excluding the solvent from the colored curable resin composition. The total amount of solids in the colored curable resin composition and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography and gas chromatography.

[0026] <Resin (B)> The resin (B) is preferably an alkali-soluble resin. Examples of the alkali-soluble resin include the following resins [K1] to [K6].

[0027] Resin [K1]: A copolymer having a structural unit derived from at least one type (a) (hereinafter, sometimes referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a structural unit derived from a monomer (b) (hereinafter, sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond. 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) (however, different from (a) and (b)) copolymerizable with (a) (hereinafter, sometimes referred to as "(c)"). 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) to which (b) is added, and a structural unit derived from (c). Resin [K5]: A copolymer having a structural unit in which (a) is added to a structural unit derived from (b) and a structural unit derived from (c). Resin [K6]: A copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic acid anhydride, and a structural unit derived from (c).

[0028] Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; 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; Bicyclounsaturated compounds containing a carboxy 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; Unsaturated dicarboxylic acid 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; Unsaturated mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids, such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate; Examples include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid.

[0029] Of these, in terms of copolymerization reactivity and the solubility of the resulting resin in an aqueous alkaline solution, (a) is preferably acrylic acid, methacrylic acid, or maleic anhydride.

[0030] (b) may be, 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 oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0031] Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (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)").

[0032] Examples of (b1) include a monomer (b1-1) (hereinafter, sometimes referred to as "(b1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, and a monomer (b1-2) (hereinafter, sometimes referred to as "(b1-2)") having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized.

[0033] 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 Examples of such styrene include 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, and 2,4,6-tris(glycidyloxymethyl)styrene.

[0034] Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000 (manufactured by Daicel Corporation)), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400 (manufactured by Daicel Corporation)), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100 (manufactured by Daicel Corporation)), 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl (meth)acrylate (3,4-epoxytricyclo[5.2.1.0 2,6 ]Decan-8-yl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-9-yl (meth)acrylate, etc.), 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyloxyethyl (meth)acrylate and the like.

[0035] (b2) is more preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group. 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, 3-ethyl-3-acryloyloxyethyloxetane, and the like.

[0036] More preferably, (b3) is a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group. Examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150 (manufactured by Osaka Organic Chemical Industry Co., Ltd.)), tetrahydrofurfuryl methacrylate, etc.

[0037] (b) is preferably (b1) in that the reliability of the obtained optical filter can be improved in terms of light resistance, heat resistance, chemical resistance, etc. Furthermore, (b) is more preferably (b1-2) in that the colored curable resin composition and the colored curable resin composition have excellent storage stability.

[0038] 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 2,6]decan-8-yl(meth)acrylate (commonly known in the art as "dicyclopentanyl(meth)acrylate" and sometimes called "tricyclodecyl(meth)acrylate"), tricyclo[5.2.1.0 2,6 ](meth)acrylic acid esters such as decene-8-yl (meth)acrylate (commonly known in the art 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, and benzyl (meth)acrylate; hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate; Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene chloro[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, bicyclounsaturated compounds such as 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; dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide; Examples of the copolymer include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.

[0039] Among these, in terms of copolymerization reactivity, light resistance, and heat resistance, (c) is preferably styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, or bicyclo[2.2.1]hept-2-ene.

[0040] In the resin [K1], the ratio of structural units derived from each of them is as follows among all structural units constituting the resin [K1]: Structural units derived from (a): 2 to 60 mol% Structural units derived from (b): 40 to 98 mol% It is preferred that Structural units derived from (a): 10 to 50 mol% Structural units derived from (b): 50 to 90 mol% It is more preferable that:

[0041] When the ratio of the structural units of the resin [K1] is within the above range, the colored curable resin composition and the colored curable resin composition tend to have excellent storage stability, developability when forming a colored pattern, and solvent resistance of the obtained optical filter.

[0042] Resin [K1] can be produced, for example, by referring to the method described in the literature "Experimental Methods of Polymer Synthesis" (written by Otsu Takayuki, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, published March 1, 1972) and the references cited in said literature.

[0043] Specifically, a method is exemplified in which a predetermined amount of (a) and (b), a polymerization initiator, a solvent, etc. are placed in a reaction vessel, and the atmosphere is deoxygenated by, for example, replacing oxygen with nitrogen, and the mixture is heated and kept warm while stirring. The polymerization initiator and solvent used here are not particularly limited, and those commonly used in the field can be used. For example, examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). The solvent may be any one that dissolves each monomer, and for example, those exemplified as solvent (E) described later can be used.

[0044] The copolymer obtained may be used as it is after the reaction, or may be used after it has been concentrated or diluted. The copolymer obtained may be used after it has been extracted as a solid (powder) by a method such as reprecipitation. In particular, by using a solvent (E) described later as a solvent during this polymerization, the solution after the reaction can be used for the preparation of the colored curable resin composition and the colored curable resin composition, and therefore the manufacturing process of the colored curable resin composition and the colored curable resin composition of this embodiment can be simplified.

[0045] In the resin [K2], the ratio of structural units derived from each of them is as follows among all structural units constituting the resin [K2]: Structural units derived from (a): 2 to 45 mol% Structural units derived from (b): 2 to 95 mol% Structural units derived from (c): 1 to 65 mol% It is preferred that Structural units derived from (a): 5 to 40 mol% Structural units derived from (b): 5 to 80 mol% Structural units derived from (c): 5 to 60 mol% It is more preferable that:

[0046] When the ratio of the structural units of the resin [K2] is within the above range, the colored curable resin composition and the colored curable resin composition tend to have excellent storage stability, developability when forming a colored pattern, and the obtained optical filter tends to have excellent solvent resistance, light resistance, heat resistance, and mechanical strength.

[0047] Resin [K2] can be produced, for example, in the same manner as described above as the method for producing resin [K1].

[0048] In the resin [K3], the ratio of structural units derived from each of them is as follows among all structural units constituting the resin [K3]: Structural units derived from (a): 2 to 60 mol% Structural units derived from (c): 40 to 98 mol% It is preferred that Structural units derived from (a): 10 to 50 mol% Structural units derived from (c): 50 to 90 mol% It is more preferable that:

[0049] Resin [K3] can be produced, for example, in the same manner as described above as the method for producing resin [K1].

[0050] Resin [K4] can be produced by obtaining a copolymer of (a) and (c), and then adding the cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and / or carboxylic acid anhydride contained in (a).

[0051] First, a copolymer of (a) and (c) is produced in the same manner as described for the production method of resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same as the ratio exemplified for resin [K3].

[0052] Next, the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms contained in (b). Following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air instead of nitrogen, and (b), a reaction catalyst for the carboxylic acid or carboxylic anhydride with the cyclic ether (e.g., tris(dimethylaminomethyl)phenol, etc.), and a polymerization inhibitor (e.g., hydroquinone, etc.) are placed in the flask, and the mixture is reacted at 60 to 130° C. for 1 to 10 hours, for example, to produce the resin [K4].

[0053] The amount of (b) used is preferably 5 to 80 moles, more preferably 10 to 75 moles, relative to 100 moles of (a). By adjusting the amount within this range, the colored curable resin composition and the colored curable resin composition tend to have a good balance of storage stability, developability when forming a pattern, and solvent resistance, light resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern. Since the reactivity of cyclic ethers is high and unreacted (b) is unlikely to remain, (b) used in the resin [K4] is preferably (b1), more preferably (b1-1).

[0054] The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass per 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 per 100 parts by mass of the total amount of (a), (b), and (c).

[0055] The reaction conditions, such as the charging method, reaction temperature and time, can be appropriately adjusted taking into consideration the production equipment, the amount of heat generated by polymerization, and the like.

[0056] Resin [K5] is produced in the first step by the same method as the above-mentioned resin [K1], to obtain a copolymer of (b) and (c). As in the above, the obtained copolymer may be used as a solution after the reaction as it is, or a concentrated or diluted solution may be used. The obtained copolymer may also be used after being extracted as a solid (powder) by a method such as reprecipitation.

[0057] The ratios of the structural units derived from (b) and (c) to the total number of moles of all structural units constituting the above copolymer are, respectively, Structural units derived from (b): 5 to 95 mol% Structural units derived from (c): 5 to 95 mol% It is preferred that Structural units derived from (b): 10 to 90 mol% Structural units derived from (c): 10 to 90 mol% It is more preferable that:

[0058] Furthermore, under the same conditions as in the manufacturing method of resin [K4], resin [K5] can be obtained by reacting the cyclic ether derived from (b) contained in the copolymer of (b) and (c) with the carboxylic acid or carboxylic anhydride contained in (a).

[0059] The amount of (a) reacted with the copolymer is preferably 5 to 80 moles per 100 moles of (b). Since the reactivity of cyclic ethers is high and unreacted (b) is unlikely to remain, (b) used in the resin [K5] is preferably (b1), more preferably (b1-1).

[0060] In resin [K5], the ratio of structural units derived from each of them is as follows among all structural units constituting resin [K5]: Structural units derived from (a) (without addition of (b)); 0 to 30 mol% Structural units obtained by adding (b) to structural units derived from (a); 5 to 95 mol% Structural units derived from (c): 5 to 95 mol% It is preferred that Structural units derived from (a) (without addition of (b)); 0 to 10 mol% Structural units obtained by adding (b) to structural units derived from (a): 15 to 90 mol% Structural units derived from (c): 10 to 85 mol% It is more preferable that Structural units derived from (a) (without addition of (b)); 0 to 5 mol% Structural units obtained by adding (b) to structural units derived from (a): 20 to 80 mol% Structural units derived from (c): 20 to 80 mol% It is even more preferred that:

[0061] The total of the structural units derived from (a) (without the addition of (b)), the structural units obtained by adding (b) to the structural units derived from (a), and the structural units derived from (c) is, for example, 90 mol % or more, preferably 95 mol % or more, more preferably 98 mol % or more, and particularly preferably 100 mol % of all the structural units constituting the resin [K5].

[0062] As the structural unit derived from (a) (without the addition of (b)), a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred. As the structural unit obtained by adding (b) to a structural unit derived from (a), a structural unit obtained by adding a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized to a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred. As the structural unit derived from (c), one or more types selected from (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group and (meth)acrylic acid esters having a cyclic saturated hydrocarbon group are preferred, and two or more types are more preferred.

[0063] The resin [K5] may be produced by referring to the production method of the resin [K4] described above, and the amount of (b) used may be more than 80 mol and 100 mol or less per 100 mol of (a).

[0064] Resin [K6] is a resin obtained by further reacting resin [K5] with a carboxylic acid anhydride. The hydroxyl group generated by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride is reacted with the carboxylic acid anhydride.

[0065] Examples of the carboxylic acid anhydride include succinic anhydride, 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, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. The amount of the carboxylic acid anhydride used is preferably 0.5 to 1 mole per mole of the amount of (a) used.

[0066] 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 acrylate / (meth)acrylic acid copolymer and other resins [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 ]Decyl acrylate / (meth)acrylic acid / benzyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate / (meth)acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6]decyl acrylate / (meth)acrylic acid / N-cyclohexylmaleimide / 2-hydroxyethyl (meth)acrylate copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane / (meth)acrylic acid / styrene copolymer, etc. [K2]; benzyl (meth)acrylate / (meth)acrylic acid copolymer, styrene / (meth)acrylic acid copolymer, etc. [K3]; benzyl (meth)acrylate / (meth)acrylic acid copolymer to which glycidyl (meth)acrylate has been added, tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymer to which glycidyl (meth)acrylate has been added, tricyclodecyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer to which glycidyl (meth)acrylate has been added, Resins such as resins to which tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate copolymers have been added [K4]; resins obtained by reacting tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate copolymers with (meth)acrylic acid, resins obtained by reacting tricyclodecyl (meth)acrylate / styrene / glycidyl (meth)acrylate copolymers with (meth)acrylic acid [K5]; resins obtained by reacting tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate copolymers with (meth)acrylic acid and then reacting the resulting resin with tetrahydrophthalic anhydride, resins obtained by reacting tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate / 2-ethylhexyl (meth)acrylate copolymers with (meth)acrylic acid and then reacting the resulting resin with succinic anhydride [K6], and the like.

[0067] Resin (B) is preferably a copolymer containing at least a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a structural unit having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond, and is more preferably Resin [K1], Resin [K2], or Resin [K6].

[0068] The polystyrene-equivalent weight average molecular weight of resin (B) is preferably 3000 to 100000, more preferably 5000 to 50000, and even more preferably 5000 to 30000. When the weight average molecular weight is within the above range, the hardness of the optical filter is improved, the residual film rate before and after development is high, the solubility of the unexposed portion in the developer is good, and the resolution of the colored pattern tends to be improved.

[0069] The dispersity of the resin (B) [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably 1.1-6, and more preferably 1.2-4.

[0070] The acid value of the resin (B) is preferably 10 to 170 mg-KOH / g, more preferably 20 to 150 mg-KOH / g, and further preferably 30 to 135 mg-KOH / g, calculated as solid content. 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 determined, for example, by titration with an aqueous potassium hydroxide solution.

[0071] The content of the resin (B) is preferably 1 to 40 mass%, more preferably 3 to 30 mass%, and further preferably 5 to 20 mass%, based on the total amount of solids in the colored curable resin composition. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the residual film ratio before and after development tend to be improved.

[0072] <Polymerizable compound (C)> The polymerizable compound (C) is a compound that can be polymerized by active radicals and / or acids generated from the photopolymerization initiator (E). The polymerizable compound (C) is a compound having a methacryloyl group. When the polymerizable compound (C) is a compound having a methacryloyl group, it is possible to provide a cured product having excellent pattern formability in the colored curable resin composition.

[0073] The polymerizable compound (C) is preferably a compound having two or more methacryloyl groups, more preferably a compound having three or more methacryloyl groups.Examples of such polymerizable compounds include trimethylolpropane trimethacrylate, pentaerythritol polymethacrylate (e.g., pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate), dipentaerythritol polymethacrylate (e.g., dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate), tripentaerythritol polymethacrylate (e.g., tripentaerythritol octamethacrylate, tripentaerythritol heptamethacrylate), tetrapentaerythritol polymethacrylate (e.g., tetrapentaerythritol decamethacrylate, tetrapentaerythritol nonamethacrylate), tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene oxide-modified pentaerythritol polymethacrylate (e.g., ethylene oxide-modified pentaerythritol trimethacrylate, ethylene oxide-modified pentaerythritol tetramethacrylate), ethylene oxide-modified dipentaerythritol polymethacrylate (e.g., ethylene oxide-modified pentaerythritol trimethacrylate, ethylene oxide-modified pentaerythritol tetramethacrylate), and the like. acrylates (e.g., ethylene oxide-modified dipentaerythritol pentamethacrylate, ethylene oxide-modified dipentaerythritol hexamethacrylate), propylene oxide-modified pentaerythritol polymethacrylates (e.g., propylene oxide-modified pentaerythritol trimethacrylate, propylene oxide-modified pentaerythritol tetramethacrylate), propylene oxide-modified dipentaerythritol polymethacrylates (e.g., propylene oxide-modified dipentaerythritol pentamethacrylate, propylene oxide-modified pentaerythritol hexamethacrylate), caprolactone-modified pentaerythritol polymethacrylate (e.g., caprolactone-modified pentaerythritol trimethacrylate, caprolactone-modified pentaerythritol tetramethacrylate), caprolactone-modified dipentaerythritol polymethacrylate (e.g., caprolactone-modified dipentaerythritol pentamethacrylate, caprolactone-modified dipentaerythritol hexamethacrylate).Among these, the polymerizable compound (C) is preferably trimethylolpropane trimethacrylate, dipentaerythritol polymethacrylate (a mixture of dipentaerythritol pentamethacrylate and dipentaerythritol hexamethacrylate), or ethylene oxide-modified dipentaerythritol polymethacrylate (a mixture of ethylene oxide-modified dipentaerythritol pentamethacrylate and ethylene oxide-modified dipentaerythritol hexamethacrylate).

[0074] The molecular weight or weight average molecular weight of the polymerizable compound (C) is preferably 150-2,900, and more preferably 250-1,500.

[0075] The content of the polymerizable compound (C) is preferably 1 to 50 mass%, more preferably 2 to 40 mass%, and further preferably 3 to 30 mass%, based on the total amount of solids in the colored curable resin composition. When the content of the polymerizable compound (C) is within the above range, the residual film ratio before and after development and the chemical resistance of the color filter tend to be improved.

[0076] <Multifunctional thiol compound (D)> The polyfunctional thiol compound (D) is a compound having two or more thiol groups, and preferably has 2 to 6 thiol groups.

[0077] Examples of the polyfunctional thiol compound (D) include trimethylolpropane tris(3-mercaptopropionate) (TMMP), pentaerythritol tetrakis(3-mercaptopropionate) (PEMP), dipentaerythritol hexakis(3-mercaptopropionate) (DPMP), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (TEMPIC), tris(3-mercaptopropyl)isocyanurate (TMPIC), ethylene glycol bis(thioglycolate) (EGTG), tetraethylene glycol bis(3-mercaptopropionate) (EGMP-4), trimethylolpropane tris(thioglycolate) (TMTG), pentaerythritol tetrakis(thioglycolate) ( Polyfunctional thiol compounds having an ester bond (-C(O)-O-) in the molecule, such as 1,4-butanedithiol, 1,6-hexanedithiol, and 1,10-decanedithiol; and polyfunctional thiol compounds not having an ester bond (-C(O)-O-) in the molecule, such as 1,4-butanedithiol, 1,6-hexanedithiol, and 1,10-decanedithiol. Among these, the polyfunctional thiol compound (D) is preferably a polyfunctional thiol compound having an ester bond (-C(O)-O-) in the molecule.

[0078] The molecular weight of the polyfunctional thiol compound (D) is preferably 100-1,000, and more preferably 120-800.

[0079] The content of the polyfunctional thiol compound (D) is more than 10% by mass based on the total amount of solids in the colored curable resin composition. When the content of the polyfunctional thiol compound (D) is within the above range, the change in film thickness before and after development in the cured product of the colored curable resin composition can be reduced, and the residual film rate can be improved. The content of the polyfunctional thiol compound (D) is preferably 12% by mass or more, more preferably 14% by mass or more, and even more preferably 16% by mass or more based on the total amount of solids in the colored curable resin composition. From the viewpoint of developability, the content of the polyfunctional thiol compound (D) is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less.

[0080] <Photopolymerization initiator (E)> The photopolymerization initiator (E) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. by the action of light and initiate polymerization, and known polymerization initiators can be used. Examples of polymerization initiators that generate active radicals include O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, and biimidazole compounds.

[0081] An O-acyloxime compound is a compound having a partial structure represented by formula (Ea). Hereinafter, * represents a bond.

[0082] [ka]

[0083] Examples of the O-acyloxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, and the like. As the O-acyloxime compound, commercially available products such as IRGACURE (registered trademark, hereinafter the same) OXE01 (N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine), IRGACURE OXE02 (N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine) (both manufactured by BASF), and N-1919 (manufactured by ADEKA Corporation) may be used.

[0084] Among these, the O-acyloxime compounds are N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine, and N-benzoyloxy-1-( At least one selected from the group consisting of N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine is preferred, and N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, or N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine is more preferred. When such an O-acyloxime compound is used, a color filter with high brightness tends to be obtained.

[0085] The alkylphenone compound is a compound having a partial structure represented by formula (e2) or a partial structure represented by formula (e3). In these partial structures, the benzene ring may have a substituent.

[0086] [ka]

[0087] Examples of the compound having a partial structure represented by formula (e2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one, etc. As the compound having a partial structure represented by formula (e2), commercially available products such as Irgacure 369, 907, and 379 (all manufactured by BASF) may be used.

[0088] Examples of compounds having a partial structure represented by formula (e3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyl dimethyl ketal.

[0089] In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (e2).

[0090] Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2 -(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, and the like.

[0091] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Commercially available products such as Irgacure 819 (manufactured by BASF) may also be used as the acylphosphine oxide compound.

[0092] Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, JP-B-48-38403 and JP-A-62-174204), and biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboalkoxy groups (see, for example, JP-A-7-10913).

[0093] Further, examples of the photopolymerization initiator (E) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(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 phenylglyoxylate, and titanocene compounds. These are preferably used in combination with the polymerization initiator aid (Ea) (especially amines) described below.

[0094] Examples of the polymerization initiator that generates an acid include onium salts such as 4-hydroxyphenyl dimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyl dimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyl dimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium hexafluoroantimonate; nitrobenzyl tosylates; and benzoin tosylates.

[0095] The photopolymerization initiator (E) is preferably a polymerization initiator containing at least one selected from the group consisting of an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a biimidazole compound, and is more preferably a polymerization initiator containing an O-acyloxime compound.

[0096] The content of the photopolymerization initiator (E) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (E) 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 can be expected to be improved.

[0097] <Polymerization initiator aid (Ea)> The polymerization initiation aid (Ea) is a compound or sensitizer used to promote the polymerization of a polymerizable compound. When the colored curable resin composition contains the polymerization initiation aid (Ea), it is usually used in combination with the polymerization initiator (E).

[0098] Examples of the polymerization initiator aid (Ea) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

[0099] Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone. As the amine compound, a commercially available product such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used. Among these, the amine compound is preferably 4,4'-bis(diethylamino)benzophenone.

[0100] Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and 2-ethyl-9,10-dibutoxyanthracene.

[0101] Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0102] Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

[0103] When these polymerization initiation aids (Ea) are used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the amount of the polymerization initiation aid (Ea) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to improve.

[0104] <Solvent (F)> The solvent (F) is not particularly limited, and a solvent commonly used in the field 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 containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (solvent containing OH in the molecule and not containing -O-, -CO-, and -COO-), aromatic hydrocarbon solvent, amide solvent, dimethyl sulfoxide, etc. can be mentioned.

[0105] Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0106] 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-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and methylanisole.

[0107] The ether ester solvents 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-methyl ... Examples of the alkyl ether acetates include ethyl methoxy-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.

[0108] 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.

[0109] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0110] Aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

[0111] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0112] Among these, the solvent (F) is preferably at least one selected from the group consisting of ether ester solvents and ether solvents, and more preferably propylene glycol monomethyl ether acetate or diethylene glycol ethyl methyl ether.

[0113] The content of the solvent (F) is preferably 70 to 95 mass%, more preferably 75 to 92 mass%, based on the total amount of the colored curable resin composition. In other words, the content of the solid content of the colored curable resin composition is preferably 5 to 30 mass%, more preferably 8 to 25 mass%, based on the total amount of the colored curable resin composition. When the content of the solvent (C) is within the above range, the flatness during coating is good, and the color density is unlikely to be insufficient when a color filter is formed, so that the display characteristics tend to be good.

[0114] When an ether ester solvent is used, the content of the ether ester solvent is preferably 10 to 100 mass %, more preferably 15 to 90 mass %, and further preferably 17 to 80 mass %, based on the total amount of the solvent.

[0115] When an ether solvent is used, the content of the ether solvent is preferably 20 to 90 mass %, more preferably 30 to 85 mass %, and further preferably 40 to 80 mass %, based on the total amount of the solvent.

[0116] <Leveling agent (G)> Examples of the leveling agent (G) include silicone surfactants, fluorine surfactants, silicone surfactants having fluorine atoms, etc. These may have a polymerizable group in the side chain.

[0117] Examples of silicone surfactants include surfactants having a siloxane bond in the molecule. Specific examples include Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (trade names, manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan, LLC).

[0118] Examples of fluorine-based surfactants include surfactants having a fluorocarbon chain in the molecule.Specific examples include Fluorad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, SC105 (manufactured by AGC Corporation (formerly Asahi Glass Co., Ltd.)), and E5844 (manufactured by Daikin Fine Chemicals Research Institute Co., Ltd.).

[0119] Examples of silicone surfactants having fluorine atoms include surfactants having a siloxane bond and a fluorocarbon chain in the molecule, such as Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

[0120] The content of the leveling agent (G) is preferably 0.001 to 0.2 mass%, more preferably 0.002 to 0.1 mass%, and even more preferably 0.01 to 0.05 mass%, based on the total amount of the colored curable resin composition. When the content of the leveling agent (G) is within the above range, the flatness of the color filter can be improved.

[0121] <Silane coupling agent (H)> Examples of the silane coupling agent (H) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- Examples of such silanes include (3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, and 3-glycidoxypropylethoxydimethylsilane.

[0122] Commercially available silane coupling agents (H) include, for example, KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, K Examples of silane coupling agents available from Shin-Etsu Chemical Co., Ltd. include BE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, and KBE-9007.

[0123] The content of the silane coupling agent (H) is preferably 0.001 to 0.2 mass %, more preferably 0.002 to 0.1 mass %, and even more preferably 0.01 to 0.05 mass %, based on the total amount of the colored curable resin composition.

[0124] <Other ingredients> The colored resin composition of the present embodiment may contain additives known in the art, such as dispersants, ultraviolet absorbers, fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents, as necessary.

[0125] The colored curable resin composition of the present embodiment can be prepared, for example, by mixing the colorant (A), the resin (B), the polymerizable compound (C), the polyfunctional thiol compound (D), the photopolymerization initiator (E), and the polymerization initiator aid (Ea), which is used as necessary, the solvent (F), the leveling agent (G), the coupling agent (H), and other components. After mixing the components, the colored curable resin composition is preferably filtered through a filter having a pore size of about 0.01 to 10 μm.

[0126] The colored curable resin composition of the present embodiment is suitably used for forming a color filter.

[0127] [Color filter and its manufacturing method] Examples of methods for producing a colored pattern from the colored curable resin composition of the present embodiment include a photolithography method, an inkjet method, and a printing method. Among these, the method for producing a colored pattern is preferably a photolithography method. The photolithography method is a method in which a colored curable resin composition is applied to a substrate, dried to form a colored coating film, and the colored coating film is exposed through a photomask and developed. In the photolithography method, a colored cured coating film, which is a cured product of the colored coating film, can be formed by not using a photomask during exposure and / or not developing. The colored pattern (pattern colored cured coating film) or colored cured coating film thus formed is the color filter of the present embodiment.

[0128] The thickness of the color filter to be produced is not particularly limited and can be appropriately adjusted depending on the purpose and use, etc. The thickness of the color filter may be, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

[0129] Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass with a silica-coated surface; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon substrates; and substrates having a thin film of aluminum, silver, or a silver / copper / palladium alloy formed thereon. On these substrates, other color filters (colored patterns or colored cured coating films), resin films, transistors, circuits, and the like may be formed.

[0130] The formation of each color pixel by photolithography can be carried out using known or commonly used equipment, conditions, etc. The formation of each color pixel by photolithography can be carried out, for example, as follows.

[0131] First, the colored curable resin composition is applied onto a substrate, and then dried by heating and drying (prebaking) and / or drying under reduced pressure to remove volatile components such as the solvent, thereby obtaining a smooth colored coating film.

[0132] Examples of the coating method include spin coating, slit coating, and slit and spin coating. When drying by heating, the temperature is preferably 30 to 120°C, and more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. When drying under reduced pressure, it is preferably performed under a pressure of 50 to 150 Pa at a temperature of 20 to 25°C.

[0133] The thickness of the colored coating film is not particularly limited, and can be appropriately selected depending on the thickness of the desired color filter.

[0134] Next, the colored coating film is exposed through a photomask for forming a desired colored pattern. The pattern of the photomask is not particularly limited, and a pattern depending on the intended use can be used.

[0135] The light source used for exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. The light source used for exposure may be, for example, a light source that cuts light less than 350 nm using a filter that cuts this wavelength range, or a light source that selectively extracts light around 436 nm, around 408 nm, and around 365 nm using a bandpass filter that extracts these wavelength ranges. Specific examples of the light source used for exposure include a mercury lamp, a light-emitting diode, a metal halide lamp, and a halogen lamp.

[0136] For exposure, it is preferable to use an exposure device such as a mask aligner and a stepper, since this allows uniform irradiation of the entire exposure surface with parallel light rays and allows accurate alignment of the photomask with the substrate on which the colored coating film is formed.

[0137] A colored pattern is formed on the substrate by contacting the exposed colored coating film (i.e., the colored cured coating film) with a developer and developing it. The unexposed parts of the colored cured coating film are dissolved in the developer and removed by development. Examples of the developer include aqueous solutions (aqueous developers) containing alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide. The concentration of the alkaline compound in these aqueous developers is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. The developer may further contain a surfactant.

[0138] Examples of the developing method include a puddle method, a dipping method, a spray method, etc. During development, the substrate may be tilted at an arbitrary angle. After development, it is preferable to wash the obtained colored pattern with water.

[0139] The obtained colored pattern is preferably post-baked. The post-baking temperature is preferably 150 to 250° C., more preferably 160 to 235° C. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

[0140] [Display devices and solid-state imaging devices] The display device of the present embodiment includes a color filter which is a colored pattern, a colored cured coating film, etc. The solid-state imaging device of the present embodiment includes a color filter which is a colored pattern, a colored cured coating film, etc.

[0141] The colored curable resin composition of the present embodiment can be used to prepare, for example, a color filter. The color filter is useful as a film for use in displays such as liquid crystal displays, electroluminescent displays, and plasma displays; and solid-state imaging devices such as CCD and CMOS sensors. EXAMPLES

[0142] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples, and can of course be practiced with appropriate modifications within the scope of the above and below spirit, all of which are included in the technical scope of the present invention. In the following, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

[0143] In the following examples, "room temperature" means 18 to 24°C.

[0144] In the following examples, the structures of the compounds were confirmed by a mass spectrometer (LC: Agilent Model 1200, MASS: Agilent Model LC / MSD6130).

[0145] The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by GPC under the following conditions. Equipment: HLC-8120GPC (Tosoh Corporation) Column: TSK-GELG2000HXL Column temperature: 40℃ y: Tetrahydrofuran Flow rate: 1.0mL / min Solid concentration of the analytical sample: 0.001 to 0.01% by mass Injection volume: 50μL Detector: RI Calibration standard materials: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

[0146] The ratio of the weight average molecular weight and the number average molecular weight (Mw / Mn) calculated in terms of polystyrene obtained above was taken as the dispersity.

[0147] (Synthesis Example 1) <Preparation of Colorant Dispersion A1> 3.3 parts of CI Pigment Green 36 and 1.0 parts of acrylic pigment dispersant were mixed with 20.0 parts of propylene glycol monomethyl ether acetate, and the pigment was thoroughly dispersed using a bead mill to obtain dispersion liquid DA1. Next, 1.4 parts of CI Pigment Yellow 150 and 0.6 parts of acrylic pigment dispersant were mixed with 9.5 parts of propylene glycol monomethyl ether acetate, and the pigment was thoroughly dispersed using a bead mill to obtain dispersion liquid DB1. Next, dispersion liquid DA1 and dispersion liquid DB1 were mixed and dispersed using a bead mill to obtain colorant dispersion liquid A1.

[0148] (Synthesis Example 2) <Preparation of Colorant Dispersion A2> 3.7 parts of CI Pigment Blue 15:6 and 0.9 parts of an acrylic pigment dispersant were mixed with 25.1 parts of propylene glycol monomethyl ether acetate, and the pigment was thoroughly dispersed using a bead mill to obtain dispersion liquid DC1. Next, 0.5 parts of Pink Base (manufactured by Taiyo Fine Chemical Co., Ltd.) and 0.2 parts of an acrylic pigment dispersant were mixed with 5.4 parts of propylene glycol monomethyl ether acetate, and the pigment was thoroughly dispersed using a bead mill to obtain dispersion liquid DD1. Next, dispersion liquid DC1 and dispersion liquid DD1 were mixed and dispersed using a bead mill to obtain colorant dispersion liquid A2.

[0149] (Synthesis Example 3) <Preparation of Resin B1> A flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube was charged with 258 parts of propylene glycol monomethyl ether acetate, which was stirred while replacing with nitrogen, and heated to 120°C. Next, a monomer mixture consisting of 90 parts of 2-ethylhexyl acrylate, 180 parts of glycidyl methacrylate, and 12 parts of dicyclopentanyl methacrylate, to which 11 parts of tert-butylperoxy-2-ethylhexanoate had been added, was dropped into the flask from the dropping funnel over 2 hours. After the dropwise addition was completed, the mixture was stirred for another 30 minutes to carry out a copolymerization reaction. Thereafter, the flask was replaced with air, and 91 parts of acrylic acid, 1.1 parts of triphenylphosphine, and 1.1 parts of methoquinone were added, and the reaction was continued at 120°C for 10 hours. Then, 18 parts of succinic anhydride were added to the reaction system, and the reaction was continued for another 30 minutes to obtain resin B1. Finally, 330 parts of propylene glycol monomethyl ether was added to the reaction solution, and then propylene glycol monomethyl ether acetate was added to give a solid concentration of 40%, to obtain a solution of resin B1 (double bond equivalent: 330 g / mol). The double bond equivalent of resin B1 was calculated by analyzing the structure of each structural unit constituting the curable resin.

[0150] (Synthesis Example 4) <Preparation of Resin B2> A suitable amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80°C with stirring. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6A mixed solution of 289 parts of a mixture of decan-9-yl acrylate (content ratio 1:1 by molar ratio) and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. Meanwhile, a solution of 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, 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 solids concentration of 35.1% and a viscosity of 125 mPa s measured with a Brookfield viscometer (23°C). The weight average molecular weight Mw of the resulting copolymer was 9.2×10 3 The resin B2 had a polydispersity of 2.08 and an acid value calculated as a solid content of 77 mg-KOH / g.

[0151] [ka]

[0152] (Example 1-1) <Preparation of Colored Curable Resin Composition> The following components were mixed to obtain a colored curable resin composition of Example 1-1. (A) Colorant: 35.7 parts of colorant dispersion A1 of Synthesis Example 1 (B) Resin: 4.5 parts of Resin B1 solution of Synthesis Example 3 (C) Polymerizable compound: TMPT (trimethylolpropane methacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) (C1) 1.9 parts (D) Polyfunctional thiol compound: TMMP (trimethylolpropane tris(3-mercaptopropionate), manufactured by SC Organic Chemical Co., Ltd.) (D1) 2.3 parts (E) Photopolymerization initiator: NCI-831 (manufactured by ADEKA Corporation) (E1) 0.5 parts (F) Solvent: Propylene glycol monomethyl ether acetate (F1) 54.8 parts (G) Leveling agent: Toray Silicone SH8400 (polyether modified silicone oil, manufactured by Toray Dow Corning Co., Ltd.) (G1) 0.1 part (H) Silane coupling agent: KBM-503 (3-methacryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.) (H1) 0.1 part

[0153] (Examples 1-2 to 1-9 and Comparative Examples 1-1 to 1-6) <Preparation of Colored Curable Resin Composition> The colored curable resin compositions of Examples 1-2 to 1-9 and Comparative Examples 1-1 to 1-6 were obtained in the same manner as in Example 1-1, except that the components and the amounts used (units: parts) of Example 1-1 were changed to the components and the amounts used (units: parts) shown in Tables 1 and 2.

[0154] (Example 2-1, Example 2-2, and Comparative Example 2-1) <Preparation of Colored Curable Resin Composition> The colored curable resin compositions of Examples 2-1, 2-2, and Comparative Example 2-1 were obtained in the same manner as in Example 1-1, except that the components and the amounts used (units: parts) of each component in Example 1-1 were changed to the components and the amounts used (units: parts) shown in Table 3.

[0155] In addition, A2, B2, C2, Cc1, D2, D3, and D4 in Tables 1, 2, and 3 are as follows. (A) Colorant: Colorant dispersion A2 of Synthesis Example 2 (B) Resin: Resin B2 solution of Synthesis Example 4 (C) Polymerizable compound: M-DPH-3PO (propylene oxide modified dipentaerythritol polymethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) (C2) M-930 (glyceryl acrylate, manufactured by Toagosei Co., Ltd.) (Cc1) (D) Multifunctional thiol compound: KarenzMT PE1 (Pentaerythritol tetrakis(3-mercaptobutyrate), manufactured by Resonac Co., Ltd.) (D2) Karenz MT BD1 (1,4-bis(3-mercaptobutyryloxy)butane, manufactured by Resonac Co., Ltd.) (D3) Karenz MT TPMB (trimethylolpropane tris(3-mercaptobutyrate), manufactured by Resonac Co., Ltd.) (D4)

[0156] Moreover, the content of (D) in Tables 1, 2, and 3 means the content of (D) based on the total amount of solids in the colored curable resin composition.

[0157] [Table 1]

[0158] [Table 2]

[0159] [Table 3]

[0160] <Evaluation of Colored Curable Resin Composition> -Evaluation of remaining film rate Each colored curable resin composition was applied by spin coating onto a 2-inch square glass substrate (Eagle 2000, Corning Incorporated), and prebaked at 85°C for 2 minutes. After cooling, the substrate was exposed to light at 100 mJ / cm2 in the air using an exposure machine (TME-150RSK, Topcon Corporation), with the distance between the substrate and a quartz glass photomask set at 50 µm. 2The substrate was irradiated with light at an exposure dose (based on 365 nm). The film thickness of the obtained colored cured coating film was measured using a film thickness measuring device (DEKTAK3, manufactured by Nippon Shinku Gijutsu Co., Ltd.) and was designated as FA (μm). A photomask on which a 10 μm line and space pattern was formed was used. After the light irradiation, the substrate was immersed and developed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 24° C. for 60 seconds. After washing with water, the substrate was post-baked in an oven at 85° C. for 30 minutes to obtain a colored pattern (patterned colored cured coating film). The film thickness of the obtained colored pattern was measured using a film thickness measuring device (DEKTAK3, manufactured by Nippon Shinku Gijutsu Co., Ltd.) and was designated as FB (μm). The remaining film ratio was calculated from the measured film thicknesses FA and FB according to the following formula. The results are shown in Tables 4, 5, and 6. Remaining film rate (%)=FB / FA×100

[0161] ·Pattern evaluation The colored patterns prepared in the above "Evaluation of film remaining ratio" were observed using a scanning electron microscope (S-4000, Hitachi, Ltd.). When the pattern line width was more than 0 nm and less than 20 nm, it was evaluated as "A" as excellent pattern formability, and when a pattern could not be formed or the pattern line width was 20 nm or more, it was evaluated as "B". The results are shown in Tables 4, 5, and 6.

[0162] [Table 4]

[0163] [Table 5]

[0164] [Table 6]

[0165] As shown in Tables 4, 5, and 6, the colored curable resin compositions of the examples, which contain a predetermined polymerizable compound and have a polyfunctional thiol compound content within a predetermined range, were superior in both the residual film rate and pattern formability before and after development to the colored curable resin compositions of the comparative examples, which do not satisfy these conditions. From these results, it was confirmed that the colored curable resin composition of the present invention can provide a cured product that is excellent in the residual film rate and pattern formability before and after development.

Claims

1. A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polyfunctional thiol compound, and a photopolymerization initiator, the polymerizable compound is a compound having a methacryloyl group, The content of the polyfunctional thiol compound is more than 10 mass% based on the total amount of solids of the colored curable resin composition. Colored curable resin composition.

2. The polymerizable compound is a compound having two or more methacryloyl groups. The colored curable resin composition according to claim 1 .

3. A color filter formed from the colored curable resin composition according to claim 1 or 2.

4. A display device comprising the color filter according to claim 3 .

5. A solid-state imaging device comprising the color filter according to claim 3 .

Images