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

Abstract

The present invention addresses the problem of providing a colored curable resin composition capable of forming a color filter having further reduced residue and improved adhesion. The present invention relates to a colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), the polymerizable compound (C) comprising a polymerizable compound (C1) having a hydroxyl value of 50 mgKOH / g to 100 mgKOH / g (inclusive) and an alkyleneoxy unit of 2 to 8 (inclusive).

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 Art

[0002] Color filters used in display devices such as liquid crystal displays, electroluminescent displays, and plasma displays, and solid-state imaging devices such as CCDs and CMOS sensors are manufactured from colored curable resin compositions. It is known that a specific polymerizable compound is used in such colored curable resin compositions (Patent Document 1).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2022-094462 Summary of the Invention

[0006] Problems to be solved by the invention

[0007] When a color filter formed from a colored curable resin composition using a conventional polymerizable compound is formed on a substrate, there are problems in that residue from the colored coating film is observed and the adhesion between the colored coating film and the substrate is insufficient.

[0008] Therefore, an object of the present invention is to provide a colored curable resin composition capable of forming a color filter having further reduced residue and improved adhesion.

[0009] Means for solving problems

[0010] The gist of the present invention that can achieve the above-mentioned object is as follows.

[0011] [1] A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).

[0012] The polymerizable compound (C) includes a polymerizable compound (C1) having a hydroxyl value of 50 mgKOH / g to 100 mgKOH / g and having 2 to 8 alkyleneoxy units.

[0013] [2] The colored curable resin composition according to [1], wherein the polymerizable compound (C1) contains a compound represented by formula (2).

[0014]

[0015] (In the formula, Y represents a hydrogen atom or a (meth)acryloyl group, and at least one Y is a (meth)acryloyl group. X represents an alkylene group having 2 to 10 carbon atoms. a to d independently represent the number of alkyleneoxy units, and a+b+c+d is 2 or more and 8 or less.)

[0016] [3] The colored curable resin composition according to [1] or [2], wherein in formula (2), the alkyleneoxy unit is represented by -CH2-CH2-O- or -CH2-CH2-CH2-O-.

[0017] [4] The colored curable resin composition according to any one of [1] to [3], wherein the colorant (A) is a red pigment selected from CI Pigment Red 149, 176, 177, 242, 254, 255, 264, 269, 272, and 291.

[0018] [5] The colored curable resin composition according to any one of [1] to [4], wherein the content of the reaction product of the (meth)acrylate compound and the secondary amine compound is 30% by mass or less relative to the total of the reaction product and the polymerizable compound.

[0019] [6] A color filter formed from the colored curable resin composition according to any one of [1] to [5].

[0020] [7] A display device comprising the color filter described in [6].

[0021] [8] A solid-state imaging device comprising the color filter described in [6].

[0022] Effects of the Invention

[0023] According to the present invention, a colored curable resin composition capable of forming a color filter having further reduced residue and improved adhesion can be provided. DETAILED DESCRIPTION

[0024] The colored curable resin composition of the present invention is characterized by comprising a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).

[0025] The polymerizable compound (C) includes a polymerizable compound (C1) having a hydroxyl value of 50 mgKOH / g to 100 mgKOH / g and having 2 to 8 alkyleneoxy units.

[0026] The colored curable resin composition of the present invention may further contain a solvent (hereinafter, sometimes referred to as a solvent (E)).

[0027] The colored curable resin composition of the present invention may further contain a polymerization initiation auxiliary (hereinafter, sometimes referred to as a polymerization initiation auxiliary (D1)).

[0028] The colored curable resin composition of the present invention may further contain a thiol compound (hereinafter, sometimes referred to as a thiol compound (T)).

[0029] The colored curable resin composition of the present invention may further contain a leveling agent (hereinafter, sometimes referred to as a leveling agent (F)).

[0030] In addition, unless otherwise specified, the compounds exemplified as the components in this specification can be used alone or in combination of two or more.

[0031] <Colorant (A)>

[0032] Examples of the colorant (A) include dyes (A1) and pigments (A2), preferably pigments (A2). These may be used alone or in combination of two or more.

[0033] Dye (A1) is not particularly limited, and known dye can be used, for example, solvent dyes, acid dyes, direct dyes, mordant dyes etc. can be enumerated.As dye, for example, the known dyes recorded in the compound, dyeing guide (color dyeing company) that are classified as dyes in color index (The Society of Dyers and Colourists publishes) can be enumerated.In addition, according to chemical structure, 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, isoindoline dyes etc. can be enumerated.Among these, preferably organic solvent soluble dyes.

[0034] Specifically, dyes having the following color index (CI) numbers are mentioned.

[0035] CI Solvent Yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 117, 162, 163, 167, 189;

[0036] 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;

[0037] CI Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 77, 86, 99;

[0038] CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

[0039] 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;

[0040] CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35; etc. CI solvent dyes,

[0041] 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;

[0042] 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;

[0043] 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;

[0044] CI Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;

[0045] 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, 1 26, 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;

[0046] 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; etc. CI acid dyes,

[0047] 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;

[0048] 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;

[0049] CI Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

[0050] CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

[0051] 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, 166, 1 67, 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;

[0052] CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82; etc. CI direct dyes,

[0053] CI Disperse Yellow 51, 54, 76;

[0054] CI Disperse Violet 26, 27;

[0055] CI disperse blue 1, 14, 56, 6; 0 and other CI disperse dyes,

[0056] CI Basic Red 1, 10;

[0057] 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;

[0058] CI Basic Violet 2;

[0059] CI Basic Red 9;

[0060] CI basic green 1; etc. CI basic dyes,

[0061] CI Reactive Yellow 2, 76, 116;

[0062] CI Reactive Orange 16;

[0063] CI Reactive Red 36; etc. CI reactive dyes,

[0064] CI Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

[0065] 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;

[0066] 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;

[0067] 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;

[0068] 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;

[0069] CI mordant green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53; etc. CI mordant dyes,

[0070] CI vat green 1; etc. CI vat dyes, etc.

[0071] These dyes may be appropriately selected according to the spectral spectrum of a desired color filter.

[0072] As the pigment (A2), known pigments can be used, for example, pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists). In addition, based on 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, isoindoline pigments, etc. are mentioned. Among these, phthalocyanine pigments, quinophthalone pigments, isoindoline pigments, etc. are preferred.

[0073] Specific examples of pigments classified as pigments include:

[0074] 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 and other yellow pigments;

[0075] CI Pigment Orange 13, 31, 34, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments;

[0076] 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 and other red pigments;

[0077] CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60 and other blue pigments;

[0078] CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments;

[0079] CI Pigment Green 7, 36, 58, 59, 62, 63 and other green pigments;

[0080] Brown pigments such as CI Pigment Brown 23 and 25;

[0081] Black pigments such as CI Pigment Black 1, 7, 31, 32, etc.;

[0082] These pigments may be appropriately selected according to the spectral spectrum of a desired color filter.

[0083] When preparing a green colored curable resin composition, the colorant (A) preferably contains at least one selected from the group consisting of yellow dyes and yellow pigments (hereinafter, these may be collectively referred to as "yellow colorants"), green dyes and green pigments (hereinafter, these may be collectively referred to as "green colorants"), and more preferably contains a yellow pigment and / or a green pigment.

[0084] Examples of yellow dyes include dyes whose hues are classified as yellow among the above-mentioned dyes, and examples of yellow pigments include pigments whose hues are classified as yellow among the above-mentioned pigments.

[0085] Among the yellow pigments, quinophthalone yellow pigments, metal-containing yellow pigments, and isoindoline yellow pigments are preferred, CI Pigment Yellow 129, 138, 139, 150, and 185 are more preferred, CI Pigment Yellow 138, 139, 150, and 185 are further preferred, and CI Pigment Yellow 138, 139, and 185 are even more preferred.

[0086] Examples of green dyes include dyes whose hues are classified as green among the above dyes, and examples of green pigments include pigments whose hues are classified as green among the above pigments.

[0087] Among green pigments, phthalocyanine pigments are preferred, more preferably at least one selected from the group consisting of copper phthalocyanine halides and zinc phthalocyanine halides, further preferably CI Pigment Green 7, 36, 58, 59, 62, and 63, and even more preferably CI Pigment Green 36, 58, and 59.

[0088] When preparing a green colored curable resin composition, the colorant (A) preferably contains a total of, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more of a yellow colorant and / or a green colorant based on 100% by mass of all colorants.

[0089] In addition, it is preferred that both a yellow colorant and a green colorant are contained. When both a yellow colorant and a green colorant are contained, the content of the yellow colorant in 100% by mass of the total of the yellow colorant and the green colorant is, for example, 10% by mass to 70% by mass, preferably 15% by mass to 60% by mass, and more preferably 20% by mass to 55% by mass.

[0090] When both a yellow colorant and a green colorant are contained, the content of the green colorant in 100 mass% of the total of the yellow colorant and the green colorant is, for example, 30 mass% to 90 mass%, preferably 40 mass% to 85 mass%, and more preferably 45 mass% to 80 mass%.

[0091] When preparing a red colored curable resin composition, the colorant (A) preferably contains at least one selected from the group consisting of red dyes and red pigments (hereinafter sometimes collectively referred to as "red colorants") and yellow colorants, and more preferably contains a yellow pigment and / or a red pigment.

[0092] Examples of the yellow colorant include the same ones as those in the case of preparing the green colored curable resin composition, and preferred embodiments are also the same.

[0093] Examples of red dyes include dyes whose hues are classified as red among the above-mentioned dyes, and examples of red pigments include pigments whose hues are classified as red among the above-mentioned pigments.

[0094] Among the red pigments, one or more selected from the group consisting of CI Pigment Red 149, 176, 177, 242, 254, 255, 264, 269, 272 and 291 are preferred, one or more selected from the group consisting of CI Pigment Red 177, 242, 254, 269, 272 and 291 are more preferred, and one or more selected from the group consisting of CI Pigment Red 254, 269, 272 and 291 are still more preferred.

[0095] When preparing a red colored curable resin composition, the colorant (A) contains, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass of a yellow colorant and / or a red colorant, based on 100% by mass of all colorants. It is also preferred that both yellow and red colorants are contained.

[0096] When the red colored curable resin composition contains a yellow colorant and / or a red colorant, the content of the red colorant relative to the total of the yellow colorant and the red colorant is, for example, 50% by mass or more and 95% by mass or less, preferably 60% by mass or more and 90% by mass or less, and more preferably 70% by mass or more and 85% by mass or less.

[0097] When preparing a blue colored curable resin composition, the colorant (A) preferably contains at least one selected from the group consisting of blue dyes and blue pigments (hereinafter sometimes collectively referred to as "blue colorants"), and more preferably contains a blue pigment.

[0098] Examples of the blue dye include dyes whose hue is classified as blue among the above-mentioned dyes, and examples of the blue pigment include pigments whose hue is classified as blue among the above-mentioned pigments.

[0099] As the blue pigment, phthalocyanine pigments are preferred, and CI Pigment Blue 15, 15:3, 15:4, 15:6, and 16 are more preferred.

[0100] When preparing a blue colored curable resin composition, it is preferred that a violet dye and a violet pigment (hereinafter, these may be collectively referred to as "violet colorant") be contained in addition to the blue colorant.

[0101] Examples of the violet dye include dyes whose hue is classified as violet among the above-mentioned dyes, and examples of the violet pigment include pigments whose hue is classified as violet among the above-mentioned pigments.

[0102] As the violet colorant, a violet pigment is preferred, and among the violet pigments, CI Pigment Violet 19, 23, and 29 are more preferred.

[0103] When preparing a blue colored curable resin composition, the colorant (A) preferably contains, for example, 30% by mass or more (preferably 50% by mass or more, more preferably 60% by mass or more) and 99% by mass or less of the blue colorant, based on 100% by mass of the total colorant. Furthermore, when a violet colorant is included, the content of the blue colorant, based on 100% by mass of the total of the blue and violet colorants, is, for example, 5% by mass or more and 95% by mass or less, preferably 10% by mass or more and 80% by mass or less, and more preferably 20% by mass or more and 60% by mass or less.

[0104] When preparing a yellow colored curable resin composition, the colorant (A) preferably contains at least one yellow colorant, more preferably contains at least one yellow pigment, and further preferably contains two or more yellow pigments.

[0105] As the yellow pigment, CI Pigment Yellow 129, 138, 139, 150, and 185 are preferred, and CI Pigment Yellow 138, 139, 150, and 185 are more preferred.

[0106] When preparing a yellow colored curable resin composition, the colorant (A) preferably contains, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 100% by mass of a yellow colorant based on 100% by mass of all colorants.

[0107] When the colored curable resin composition contains a solvent (E), a colorant-containing liquid containing the colorant (A) and the solvent (E) can be prepared in advance, and then the colored curable resin composition can be prepared using this colorant-containing liquid. When the colorant (A) is insoluble in the solvent (E), for example, when the colorant (A) contains the pigment (A2), the colorant-containing liquid can be prepared by dispersing the colorant (A) in the solvent (E) and mixing them. The colorant-containing liquid may contain a portion or all of the solvent (E) contained in the colored curable resin composition.

[0108] The solid content in the colorant-containing liquid is less than 100 mass % relative to the total amount of the colorant-containing liquid, preferably from 1 mass % to 80 mass %, more preferably from 2 mass % to 70 mass %, and even more preferably from 5 mass % to 65 mass %.

[0109] The content of the colorant (A) in the colorant-containing liquid is less than 100 mass%, preferably from 0.5 mass% to 80 mass%, more preferably from 1 mass% to 70 mass%, and even more preferably from 2.5 mass% to 65 mass%, relative to the total amount of solids in the colorant-containing liquid.

[0110] The colorant (A) may be subjected to, as necessary, rosin treatment; surface treatment using derivatives introducing acidic or basic groups; grafting treatment onto the surface of the colorant (A) using a polymer compound; micronization treatment using a sulfuric acid micronization method, a salt milling method, or the like; washing treatment to remove impurities using an organic solvent, water, or the like; or treatment to remove ionic impurities using an ion exchange method or the like. The particle size of the colorant (A) is preferably substantially uniform.

[0111] By adding a dispersant to the colorant (A) and performing a dispersion treatment, the colorant (A) can be uniformly dispersed in the solution. When two or more colorants (A) are used in combination, each can be dispersed individually or a plurality of them can be mixed and dispersed.

[0112] As a dispersant, for example, surfactants can be mentioned, which can be any surfactant among cationic, anionic, nonionic and amphoteric. Specifically, surfactants such as polyester, polyamine and acrylic acid can be mentioned. These dispersants can be used alone, or two or more can be used in combination. As a dispersant, if expressed by trade name, KP (Shin-Etsu Chemical Industry (Strain) system), FLOWLEN (Kyoeisha Chemical (Strain) system), SOLSPERSE (registered trademark) (Zeneca (Strain) system), EFKA (registered trademark) (BASF company system), AJISPER (registered trademark) (Ajinomoto Fine-Techno (Strain) system) and Disperbyk (registered trademark) (BYK-Chemie (Strain) system), BYK (registered trademark) (BYK-Chemie (Strain) system) etc. can be mentioned. In addition, as a dispersant, resin (B) described later (preferably at least one selected from resins [K2] and [K6]) can be used.

[0113] When a dispersant is used, the amount of the dispersant (solid content) used is generally from 1 part by mass to 10,000 parts by mass, preferably from 5 parts by mass to 5,000 parts by mass, more preferably from 10 parts by mass to 1,000 parts by mass, and even more preferably from 15 parts by mass to 800 parts by mass, relative to 100 parts by mass of the colorant (A) in the colorant-containing liquid. When the amount of the dispersant used is within the aforementioned range, a more uniformly dispersed colorant-containing liquid (hereinafter sometimes referred to as a colorant dispersion or pigment dispersion) tends to be obtained.

[0114] When a colorant-containing liquid containing the colorant (A) and the solvent (E) is prepared in advance and then used to prepare a colored curable resin composition, the colorant-containing liquid may contain a portion or all, preferably a portion, of the resin (B) contained in the colored curable resin composition. By pre-incorporating the resin (B), the dispersion stability of the colorant-containing liquid can be further improved.

[0115] When the colorant-containing liquid contains a resin (B), the content of the resin (B) relative to 100 parts by mass of the colorant (A) in the colorant-containing liquid is, for example, from 10 parts by mass to 10,000 parts by mass, preferably from 20 parts by mass to 5,000 parts by mass, and more preferably from 25 parts by mass to 2,500 parts by mass.

[0116] The content of the colorant (A) in the total solid content of the colored curable resin composition is preferably from 1% by mass to 93% by mass, more preferably from 10% by mass to 91% by mass, even more preferably from 15% by mass to 89% by mass, and even more preferably from 18% by mass to 87% by mass. When the content of the colorant (A) is within the aforementioned range, the color density of the resulting color filter is sufficient, and the required amount of resin (B) can be contained in the composition, thereby enabling the formation of a pattern with sufficient mechanical strength, which is preferred.

[0117] As used herein, 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.

[0118] <Resin (B)>

[0119] The resin (B) (also referred to as a binder 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].

[0120] Resin [K1]: A copolymer comprising a structural unit derived from at least one monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as "(a)"), and a structural unit 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)");

[0121] Resin [K2]: A copolymer having structural units derived from the aforementioned (a), structural units derived from the aforementioned (b), and structural units derived from a monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter sometimes referred to as "(c)");

[0122] Resin [K3]: a copolymer having a structural unit derived from the aforementioned (a) and a structural unit derived from the aforementioned (c);

[0123] Resin [K4]: a copolymer having a structural unit obtained by adding the aforementioned (b) to the structural unit derived from the aforementioned (a) and a structural unit derived from the aforementioned (c);

[0124] Resin [K5]: a copolymer having a structural unit obtained by adding the structural unit derived from the aforementioned (a) to the structural unit derived from the aforementioned (b) and a structural unit derived from the aforementioned (c);

[0125] Resin [K6]: A copolymer having a structural unit obtained by adding the aforementioned (a) to the structural unit derived from the aforementioned (b) and further adding a carboxylic acid anhydride, and a structural unit derived from the aforementioned (c).

[0126] Specific examples of the monomer (a) include:

[0127] Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;

[0128] 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;

[0129] 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;

[0130] 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;

[0131] 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;

[0132] Unsaturated acrylic acid esters containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid; and the like.

[0133] Among these, 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 alkaline aqueous solution.

[0134] In addition, in this specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions such as "(meth)acryloyl" and "(meth)acrylate" have the same meaning.

[0135] Monomer (b) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (e.g., at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Monomer (b) preferably comprises a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0136] As monomer (b), for example, there can be mentioned a monomer (b1) having an ethylene oxide 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)"), a monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), etc.

[0137] As monomer (b1), for example, there can be mentioned a monomer (b1-1) having a structure in which a straight-chain 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)").

[0138] Examples of the monomer (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(glycidyloxymethyl) ) styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, and the like.

[0139] Examples of the monomer (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide (registered trademark) 2000; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer (registered trademark) A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer (registered trademark) M100; manufactured by Daicel Co., Ltd.), compounds represented by formula (I), and compounds represented by formula (II).

[0140]

[0141] [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.

[0142] X a and X b Indicates a single bond, *-R c -,*-R c -O-, *-R c -S- or *-R c -NH-.

[0143] R c It represents an alkanediyl group having 1 to 6 carbon atoms.

[0144] * indicates the bond with O.]

[0145] 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.

[0146] Examples of the alkyl group in which a hydrogen atom is substituted by 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.

[0147] 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.

[0148] 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.

[0149] As X a and X b , preferably include a single bond, methylene, ethylene, *-CH2-O- and *-CH2CH2-O-, more preferably include a single bond, *-CH2CH2-O- (* represents a bond to O).

[0150] 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 formula (I-11) to formula (I-15) are preferred, and compounds represented by formula (I-1), formula (I-7), formula (I-9), or formula (I-15) are more preferred.

[0151]

[0152]

[0153] 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 formula (II-11) to formula (II-15) are preferred, and compounds represented by formula (II-1), formula (II-7), formula (II-9), or formula (II-15) are more preferred.

[0154]

[0155] 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 content ratio [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.

[0156] As monomer (b2), a monomer having an oxetane group and a (meth)acryloyloxy group is more preferred. As monomer (b2), 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-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, etc. can be mentioned.

[0157] Monomer (b3) is more preferably a monomer having a tetrahydrofuranyl group and a (meth)acryloyloxy group. Specific examples of monomer (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

[0158] Monomer (b) is preferably monomer (b1) from the perspective of further improving the reliability of the obtained color filter, such as heat resistance and chemical resistance, and more preferably monomer (b1-2) from the perspective of excellent storage stability of the colored curable resin composition.

[0159] Examples of the monomer (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 the technical field, it is commonly known as "dicyclopentanyl (meth)acrylate". In addition, it is sometimes called "tricyclodecyl (meth)acrylate"), tricyclo[5.2.1.0 2,6 ] decane-9-yl ester, (meth) acrylic acid tricyclo[5.2.1.0 2,6 ] decen-8-yl ester (in the art, commonly known as "dicyclopentenyl (meth)acrylate"), tricyclo[5.2.1.0 2,6 (Meth)acrylates such as decen-9-yl acrylate, dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate, and phenoxybenzyl (meth)acrylate;

[0160] (Meth)acrylates containing a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

[0161] Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;

[0162] 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-dimethoxy Bicyclic unsaturated compounds such as bicyclo[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;

[0163] Dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, 3-maleimidobenzoic acid-N-succinimidyl ester, 4-maleimidobutyric acid-N-succinimidyl ester, 6-maleimidocaproic acid-N-succinimidyl ester, 3-maleimidopropionic acid-N-succinimidyl ester and N-(9-acridinyl)maleimide;

[0164] Aromatic compounds containing vinyl groups such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene and p-methoxystyrene; nitriles containing vinyl groups such as (meth)acrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; amides containing vinyl groups such as (meth)acrylamide; esters such as vinyl acetate; dienes such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene; etc.

[0165] Among these, styrene, vinyltoluene, 2-ethylhexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 ] decane-8-yl ester, (meth) acrylic acid tricyclo[5.2.1.0 2,6 ] decane-9-yl ester, (meth) acrylic acid tricyclo[5.2.1.0 2,6]Decen-8-yl ester, (meth) acrylic acid tricyclo[5.2.1.0 2,6 ] decen-9-yl ester, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene and benzyl (meth)acrylate, phenoxybenzyl (meth)acrylate, etc., more preferably 2-ethylhexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 ]Decen-8-yl ester, (meth) acrylic acid tricyclo[5.2.1.0 2,6 ]9-decenyl ester, N-cyclohexylmaleimide, phenoxybenzyl (meth)acrylate.

[0166] In the resin [K1], the ratio of the structural units derived from each of the above among all the structural units constituting the resin [K1] is preferably:

[0167] Structural units derived from (a): 2 to 60 mol%

[0168] Structural units derived from (b): 40 to 98 mol%

[0169] More preferably:

[0170] Structural units derived from (a): 10 to 50 mol%

[0171] Structural units derived from (b): 50 to 90 mol%.

[0172] 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.

[0173] Resin [K1] can be produced, for example, by referring to the method described in the document "Experimental Methods for Polymer Synthesis" (High-molecular Synthesis No. Ōtsu Takayuki Publishing Co., Ltd., Chemical Dojin, 1st edition, 1st print, published on March 1, 1972) and the cited documents described in the document.

[0174] Specifically, the following method can be mentioned: a predetermined amount of (a) and (b), a polymerization initiator and a solvent are added to a reaction vessel, for example, oxygen is replaced with nitrogen to form a deoxygenated atmosphere, and heating and heat preservation are performed while stirring. It should be noted that the polymerization initiator and solvent used here are not particularly limited, and substances commonly used in the art can be used. For example, as a polymerization initiator, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, etc.) can be mentioned. As a solvent, as long as each monomer is dissolved, the organic solvent (E) of the colored curable resin composition of the present invention and the solvents described below can be mentioned.

[0175] The resulting copolymer may be used directly as a post-reaction solution, as a concentrated or diluted solution, or as a solid (powder) obtained by reprecipitation or other methods. In particular, by using the solvent contained in the colored curable resin composition of the present invention as the solvent during the polymerization, the post-reaction solution can be used directly for the preparation of the colored curable resin composition of the present invention, thereby simplifying the production process of the colored curable resin composition of the present invention.

[0176] In the resin [K2], the ratio of the structural units derived from each of the above among all the structural units constituting the resin [K2] is preferably:

[0177] Structural units derived from (a): 2 to 45 mol%

[0178] Structural units derived from (b): 2 to 95 mol%

[0179] Structural units derived from (c): 1 to 65 mol%

[0180] More preferably:

[0181] Structural units derived from (a): 5 to 40 mol%

[0182] Structural units derived from (b): 5 to 80 mol%

[0183] Structural units derived from (c): 5 to 60 mol%.

[0184] 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.

[0185] The resin [K2] can be produced, for example, in the same manner as described as the method for producing the resin [K1].

[0186] In the resin [K3], the ratio of the structural units derived from each of the above among all the structural units constituting the resin [K3] is preferably:

[0187] Structural units derived from (a): 2 to 60 mol%

[0188] Structural units derived from (c): 40 to 98 mol%

[0189] More preferably:

[0190] Structural units derived from (a): 10 to 50 mol%

[0191] Structural units derived from (c): 50 to 90 mol%.

[0192] The resin [K3] can be produced, for example, in the same manner as described as the method for producing the resin [K1].

[0193] The resin [K4] can be produced by obtaining a copolymer of (a) and (c), and adding the cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and / or carboxylic anhydride contained in (a).

[0194] 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 is preferably the same as that exemplified for resin [K3].

[0195] 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 copolymer.

[0196] After producing the copolymer of (a) and (c), 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), and a polymerization inhibitor (e.g., hydroquinone) are added to the flask and reacted at, for example, 60 to 130° C. for 1 to 10 hours to produce resin [K4].

[0197] The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). Setting the amount within this range tends to improve the storage stability of the colored curable resin composition, the developability during pattern formation, and the balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern. Since cyclic ethers are highly reactive and unreacted (b) is less likely to remain, (b1) is preferred as the (b) used in resin [K4], and (b1-1) is more preferred.

[0198] The reaction catalyst is preferably used in an amount of 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b), and (c). The polymerization inhibitor is preferably used in an amount of 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b), and (c).

[0199] The reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the heat generated by polymerization, etc. It should be noted that the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the heat generated by polymerization, etc., similarly to the polymerization conditions.

[0200] Regarding resin [K5], as a first step, a copolymer of (b) and (c) is obtained in the same manner as in the production method of resin [K1]. As described above, the obtained copolymer may be used directly as a solution after the reaction, or after a concentrated or diluted solution, or after being obtained as a solid (powder) by a method such as reprecipitation.

[0201] The ratio of the structural units derived from (b) and (c) relative to the total number of moles of all structural units constituting the copolymer is preferably:

[0202] Structural units derived from (b): 5 to 95 mol%

[0203] Structural units derived from (c): 5 to 95 mol%

[0204] More preferably:

[0205] Structural units derived from (b): 10 to 90 mol%

[0206] Structural units derived from (c): 10 to 90 mol%.

[0207] Furthermore, resin [K5] can be 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 those in the production method of resin [K4].

[0208] The amount of (a) to be reacted with the copolymer is preferably 5 to 100 mol per 100 mol of (b). (b) (b1) is preferred, and (b1-1) is more preferred, as the (b) used in the resin [K5], because the cyclic ether has high reactivity and is less likely to leave unreacted (b).

[0209] Resin [K6] is obtained by reacting resin [K5] with a polycarboxylic acid and / or a carboxylic anhydride, and further reacting the polycarboxylic acid and / or a carboxylic anhydride with the hydroxyl groups generated by the reaction of the cyclic ether from (b) with the carboxylic acid or carboxylic anhydride from (a).

[0210] Examples of the polycarboxylic acid include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, and triacrylic acid. Examples of the carboxylic 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, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride. The amount of the polycarboxylic acid and / or carboxylic anhydride used is preferably 0.05 to 1 mol, more preferably 0.1 to 0.5 mol, relative to 1 mol of the amount of (a) used.

[0211] Specific examples of the resin (B) include:

[0212] (Meth) acrylate 3,4-epoxycyclohexyl methyl ester / (meth) acrylic acid copolymer, acrylic acid 3,4-epoxy tricyclo[5.2.1.0 2,6 ] Decyl ester / (meth)acrylic acid copolymer and other resins [K1];

[0213] 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 ester / (meth) acrylic acid / N-cyclohexyl maleimide copolymer, acrylic acid 3,4-epoxy tricyclo[5.2.1.0 2,6 ] Decyl ester / (meth)acrylic acid / phenoxybenzyl(meth)acrylate copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane / (meth)acrylic acid / styrene copolymer and other resins [K2];

[0214] Resins such as benzyl (meth)acrylate / (meth)acrylic acid copolymer and styrene / (meth)acrylic acid copolymer [K3];

[0215] Resins obtained by adding glycidyl (meth)acrylate to a benzyl (meth)acrylate / (meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to a tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to a tricyclodecyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, etc. [K4];

[0216] Resins such as a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate with (meth)acrylic acid, and a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate / styrene / glycidyl (meth)acrylate with (meth)acrylic acid [K5];

[0217] Resins such as a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate with (meth)acrylic acid and further reacting it with tetrahydrophthalic anhydride, a resin obtained by reacting a copolymer of 2-ethylhexyl (meth)acrylate / dicyclopentanyl (meth)acrylate / glycidyl (meth)acrylate with (meth)acrylic acid and further reacting it with succinic anhydride, and a resin obtained by reacting a copolymer of 2-ethylhexyl (meth)acrylate / tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate with (meth)acrylic acid and further reacting it with succinic anhydride [K6]; and the like.

[0218] The resin (B) is more preferably the resin [K2] and the resin [K6], and particularly preferably the resin [K6].

[0219] The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. When the molecular weight is within the aforementioned 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 is improved.

[0220] 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.

[0221] The acid value of the resin (B) is preferably 20 to 170 mg-KOH / g, more preferably 25 to 150 mg-KOH / g, and even more preferably 30 to 135 mg-KOH / g, calculated as solids content. The acid value is 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.

[0222] The content of the resin (B) is preferably 1 to 50% by mass, more preferably 2 to 45% by mass, and even more preferably 3 to 40% by mass relative to the total solid content. When the content of the resin (B) is within the aforementioned range, a colored pattern can be formed, and the resolution and residual film rate of the colored pattern tend to be improved.

[0223] <Polymerizable Compound (C)>

[0224] The polymerizable compound (C) is a compound that can be polymerized by active radicals and / or acids generated by the polymerization initiator (D). Examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and are preferably (meth)acrylate compounds or modified products thereof (e.g., alkylene oxide-modified products).

[0225] The polymerizable compound (C) includes a polymerizable compound (C1) having a hydroxyl value of 50 mgKOH / g to 100 mgKOH / g and having 2 to 8 alkyleneoxy units. The polymerizable compound (C1) may be used alone or in combination of two or more.

[0226] The polymerizable compound (C1) preferably has a hydroxyl value of 55 mgKOH / g or more and 95 mgKOH / g or less, more preferably 60 mgKOH / g or more and 90 mgKOH / g or less, further preferably 65 mgKOH / g or more and 85 mgKOH / g or less, and even more preferably 70 mgKOH / g or more. If the hydroxyl value is less than 50 mgKOH / g, there is a concern that the amount of residue increases and the adhesion is reduced. If the hydroxyl value exceeds 100 mgKOH / g, there is a concern that the adhesion is reduced. When a plurality of polymerizable compounds (C1) are included, the hydroxyl value may be an average hydroxyl value.

[0227] The hydroxyl value can be measured as follows: according to JIS K 0070-1992, an acetylating agent is added to a sample, the sample is heated in a glycerol bath, and after cooling, a phenolphthalein solution is added as an indicator, and the sample is titrated with a potassium hydroxide ethanol solution.

[0228] In the polymerizable compound (C1), the number of alkyleneoxy units is preferably 2 to 7, more preferably 2 to 6, even more preferably 3 to 6, and even more preferably 3 to 5. An alkyleneoxy unit is a divalent group consisting of one oxygen atom and an alkylene group. Preferred polymerizable compounds (C1) are those in which the alkyleneoxy units are bonded to a polyol.

[0229] The polymerizable compound (C1) preferably includes a structure derived from a pentaerythritol compound, and more preferably includes a compound represented by formula (2).

[0230]

[0231] (In the formula, Y represents a hydrogen atom or a (meth)acryloyl group, and at least one Y is a (meth)acryloyl group. X represents an alkylene group having 2 to 10 carbon atoms. a to d independently represent the number of alkyleneoxy units, and a+b+c+d is 2 or more and 8 or less.)

[0232] In formula (2), four Ys may be (meth)acryloyl groups; one Y may be a hydrogen atom and three Ys may be (meth)acryloyl groups; two Ys may be hydrogen atoms and two Ys may be (meth)acryloyl groups; or a mixture thereof may be used.

[0233] Among them, the compound represented by formula (2) is preferably a mixture of a compound in which four Ys are (meth)acryloyl groups and a compound in which three Ys are (meth)acryloyl groups and one Y is a hydrogen atom.

[0234] Examples of the alkylene group represented by X include alkylene groups such as ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene.

[0235] X is preferably an alkylene group having 2 to 8 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms, and even more preferably an alkylene group having 2 to 4 carbon atoms.

[0236] Regarding a to d representing the number of alkyleneoxy units, a+b+c+d is preferably 2 or more and 7 or less, more preferably 2 or more and 6 or less, further preferably 3 or more and 6 or less, and even more preferably 3 or more and 5 or less.

[0237] Each of a to d is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, further preferably an integer of 1 or 2, and still more preferably 1.

[0238] In formula (2), the alkyleneoxy unit is preferably represented by -CH2-CH2-O-, -CH2-CH2-CH2-O-, -CH2-CH2-CH2-CH2-O-, -CH2-CH2-CH2-CH2-CH2-O-, -CH2-CH2-CH2-CH2-CH2-CH2-O-, or -CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-O-, more preferably by -CH2- It is represented by CH2-O-, -CH2-CH2-CH2-O-, -CH2-CH2-CH2-CH2-O-, or -CH2-CH2-CH2-CH2-CH2-CH2-O-, and is further preferably represented by -CH2-CH2-O-, -CH2-CH2-CH2-O-, or -CH2-CH2-CH2-CH2-O-, and is further preferably represented by -CH2-CH2-O- or -CH2-CH2-CH2-O-.

[0239] The alkyleneoxy units contained in formula (2) may all be the same alkyleneoxy units or different alkyleneoxy units, but are preferably all the same alkyleneoxy units.

[0240] When the polymerizable compound (C1) contains two or more compounds having different numbers of (meth)acryloyl groups, from the viewpoint of satisfying the desired hydroxyl value range, the molar ratio [(C1-1) / (C1-2)] of the polymerizable compound (C1-1) having the largest number of (meth)acryloyl groups (preferably 4) to the polymerizable compound (C1-2) having a different number of (meth)acryloyl groups (preferably 3) from the polymerizable compound (C1-1) is, for example, 50 / 50 to 99 / 1, preferably 55 / 45 to 90 / 10, more preferably 60 / 40 to 85 / 15, and even more preferably 65 / 35 to 80 / 20.

[0241] The polymerizable compound (C) may further include a polymerizable compound (C2) having a hydroxyl value of 0 mgKOH / g to 500 mgKOH / g and having less than 2 alkyleneoxy units.

[0242] The polymerizable compound (C2) preferably has a hydroxyl value of 1 mgKOH / g to 450 mgKOH / g, more preferably 5 mgKOH / g to 400 mgKOH / g, further preferably 10 mgKOH / g to 350 mgKOH / g, and even more preferably 20 mgKOH / g to 300 mgKOH / g.

[0243] The polymerizable compound (C2) preferably contains 1 or less alkyleneoxy units, and more preferably contains 0 alkyleneoxy units.

[0244] The polymerizable compound (C2) preferably contains at least one selected from the group consisting of compounds represented by formula (3) and compounds represented by formula (4). The polymerizable compound (C2) may be one kind or a combination of two or more kinds.

[0245]

[0246] (In the formula, Y represents a hydrogen atom or a (meth)acryloyl group. At least one Y is a (meth)acryloyl group.)

[0247]

[0248] (In the formula, Y represents a hydrogen atom or a (meth)acryloyl group. At least one Y is a (meth)acryloyl group.)

[0249] In formula (3), four Ys may be (meth)acryloyl groups; three Ys may be (meth)acryloyl groups and one Y may be a hydrogen atom; two Ys may be (meth)acryloyl groups and two Ys may be hydrogen atoms; one Y may be (meth)acryloyl group and three Ys may be hydrogen atoms; or a mixture of two or more selected from these.

[0250] Among them, the compound represented by formula (3) is preferably a mixture of the following compounds: a compound in which 4 Ys are (meth)acryloyl groups; a compound in which 3 Ys are (meth)acryloyl groups and 1 Y is a hydrogen atom; a compound in which 2 Ys are (meth)acryloyl groups and 2 Ys are hydrogen atoms; and a compound in which 1 Y is a (meth)acryloyl group and 3 Ys are hydrogen atoms.

[0251] In formula (4), 6 Ys may be (meth)acryloyl groups; 5 Ys may be (meth)acryloyl groups and 1 Y may be a hydrogen atom; 4 Ys may be (meth)acryloyl groups and 2 Ys may be hydrogen atoms; 3 Ys may be (meth)acryloyl groups and 3 Ys may be hydrogen atoms; 2 Ys may be (meth)acryloyl groups and 4 Ys may be hydrogen atoms; 1 Y may be (meth)acryloyl groups and 5 Ys may be hydrogen atoms; or a mixture of two or more selected from these.

[0252] Among them, the compound represented by formula (4) is preferably a mixture of a compound in which six Ys are (meth)acryloyl groups and a compound in which five Ys are (meth)acryloyl groups and one Y is a hydrogen atom.

[0253] Examples of commercially available products of the polymerizable compounds (C1) and (C2) include ATM-4EL and A-9530 (Shin-Nakamura Chemical Co., Ltd.), and Aronix MT-3545 and MT-3548 (Toagosei Co., Ltd.).

[0254] When the polymerizable compound (C) contains the polymerizable compound (C1) and the polymerizable compound (C2), the mass ratio of the polymerizable compound (C1) / the polymerizable compound (C2) is, for example, 1 to 20, preferably 1.2 to 10, more preferably 1.5 to 5, and even more preferably 1.8 to 3.5.

[0255] The polymerizable compound (C) of the present invention may contain another polymerizable compound (C3) as long as it contains the polymerizable compound (C1) and / or the polymerizable compound (C2) and exhibits the effects of the present invention.

[0256] As other polymerizable compounds (C3), the following compounds can be mentioned.

[0257] Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl pyrrolidone.

[0258] Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di(meth)acrylate.

[0259] Examples of the polymerizable compound having three or more ethylenically unsaturated bonds include trimethylolpropane tri(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, pentaerythritol deca(meth)acrylate, pentaerythritol nona(meth)acrylate, and tris(2-(meth)acryloyloxyethyl)isocyanurate.

[0260] The weight average molecular weight of the polymerizable compound (C3) is preferably 50 to 4,000, more preferably 70 to 3,500, further preferably 100 to 3,000, further preferably 150 to 2,900, particularly preferably 250 to 1,500.

[0261] The content of the polymerizable compounds (C1), (C2) and (C3) in 100% by mass of the polymerizable compound (C) (preferably the content of the polymerizable compounds (C1) and (C2) or the content of the polymerizable compound (C1)) is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and even more preferably 100% by mass.

[0262] The content of the polymerizable compound (C) relative to the total solid content of the colored curable resin composition can be, for example, 1% by mass or more and 99% by mass or less, preferably 3% by mass or more and 90% by mass or less, more preferably 5% by mass or more and 80% by mass or less, and even more preferably 7% by mass or more and 70% by mass or less.

[0263] In the present invention, the content of the reaction product of the (meth)acrylate compound and the secondary amine compound is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 0% by mass, relative to the total of the reaction product and the polymerizable compound.

[0264] <Polymerization Initiator (D)>

[0265] The polymerization initiator (D) may be any compound that generates active radicals, an acid, or the like under the action of light or heat to initiate polymerization.

[0266] Examples of the polymerization initiator (D) include O-acyl oxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.

[0267] The O-acyloxime compound is a compound having a partial structure represented by formula (d-1).

[0268] In the formula, * represents a connecting bond.

[0269]

[0270] Examples of the O-acyl oxime compound include N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3 ,3-dimethyl-2,4-dioxolanemethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine, N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine, etc. Commercially available products such as Irgacure OXE01 (N-benzoyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine), Irgacure OXE02 (N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine) (both manufactured by BASF), and N-1919 (manufactured by ADEKA) can be used. Among them, the O-acyl oxime compound is preferably selected from N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine and N At least one of the group consisting of N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, more preferably N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, and N-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine. These O-acyl oxime compounds tend to provide optical filters with high brightness.

[0271] The alkylphenone compound is a compound having a partial structure represented by formula (d-2) or a partial structure represented by formula (d-3). In these partial structures, the benzene ring may have a substituent. In the formula, * represents a connecting bond.

[0272]

[0273] Examples of the compound having a partial structure represented by formula (d-2) include 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]butane-1-one. Commercially available products such as Irgacure 369, 907, and 379 (all manufactured by BASF) can be used.

[0274] Examples of the compound having a partial structure represented by formula (d-3) 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 benzil dimethyl ketal.

[0275] From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (d-2).

[0276] 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, etc.

[0277] 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.

[0278] 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 No. 6-75372 and Japanese Patent Application Laid-Open No. 6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole. (2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (see, for example, Japanese Patent Publication No. 48-38403 and Japanese Patent Application Laid-Open No. 62-174204), and biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with alkoxycarbonyl groups (see, for example, Japanese Patent Application Laid-Open No. 7-10913). Among these, compounds represented by the following formulas and mixtures thereof are preferred.

[0279]

[0280] 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, benzil, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with the polymerization initiator aid (D1) described below (particularly amines).

[0281] Examples of the polymerization initiator that generates an acid 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.

[0282] The polymerization initiator (D) is preferably a polymerization initiator comprising at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a biimidazole compound. A polymerization initiator comprising an O-acyloxime compound and / or a biimidazole compound is more preferred, and a polymerization initiator comprising an O-acyloxime compound is even more preferred.

[0283] The content of the polymerization initiator (D) is preferably from 0.1 to 30 parts by mass, more preferably from 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 aforementioned range, there is a tendency to achieve higher sensitivity and shorten exposure time, thereby improving the productivity of the optical filter.

[0284] <Polymerization initiator aid (D1)>

[0285] The polymerization initiator aid (D1) is a compound or sensitizer for accelerating the polymerization of the polymerizable compound (C) which is initiated by the polymerization initiator (D). When the polymerization initiator aid (D1) is included, it is usually used in combination with the polymerization initiator (D).

[0286] Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

[0287] 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. Preferred examples include 4,4'-bis(diethylamino)benzophenone. Commercially available amine compounds such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

[0288] 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.

[0289] Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0290] Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

[0291] When using these polymerization initiation aids (D1), the content thereof is preferably from 0.1 to 30 parts by mass, and more preferably from 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) contained in the colored curable resin composition.

[0292] <Solvent (E)>

[0293] The solvent (E) is not particularly limited, and any solvent commonly used in the art can be used.

[0294] Examples of the solvent (E) include ester solvents (solvents containing -COO- and no -O- in the molecule), ether solvents (solvents containing -O- and no -COO- in the molecule), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and no -COO- in the molecule), alcohol solvents (solvents containing OH and no -O-, -CO-, and -COO- in the molecule), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide. Two or more of these solvents may be used in combination.

[0295] 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.

[0296] 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, phenethyl ether, and methyl anisole.

[0297] 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, diethylene glycol monobutyl ether acetate, and dipropylene glycol methyl ether acetate.

[0298] 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.

[0299] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol.

[0300] Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

[0301] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0302] As the solvent (E), propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and cyclohexanone are preferred, and propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether are more preferred.

[0303] In the case of including a solvent (E), relative to the total amount of the colored curable resin composition, the content of the solvent (E) is usually 99.99% by mass or less, preferably 40% by mass or more and 99% by mass or less, more preferably 50% by mass or more and 97% by mass or less, further preferably 70% by mass or more and 96% by mass or less, and further preferably 73% by mass or more and 95% by mass or less. In other words, the total amount of the solid content of the colored curable resin composition is usually 0.01% by mass or more, preferably 1% by mass or more and 60% by mass or less, more preferably 3% by mass or more and 50% by mass or less, further preferably 4% by mass or more and 30% by mass or less, and further preferably 5% by mass or more and 27% by mass or less. If the content of the solvent (E) is within the aforementioned range, the flatness during coating becomes good, and the color concentration is not insufficient when forming a color filter, so there is a tendency for display characteristics to become good.

[0304] <Thiol Compound (T)>

[0305] The colored curable resin composition of the present invention may contain a thiol compound (T). The thiol compound (T) is a compound having a sulfanyl group (-SH) in the molecule.

[0306] Examples of the compound having one mercapto group in the molecule include 2-mercaptooxazole, 2-mercaptothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptonicotinic acid, 2-mercaptopyridine, 2-mercaptopyridin-3-ol, 2-mercaptopyridine-N-oxide, 4-amino-6-hydroxy-2-mercaptopyrimidine, 4-amino-6-hydroxy-2-mercaptopyrimidine, 4-amino-2-mercaptopyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy-2-mercaptopyrimidine, 4,6-diamino- -2-mercaptopyrimidine, 2,4-diamino-6-mercaptopyrimidine, 4,6-dihydroxy-2-mercaptopyrimidine, 4,6-dimethyl-2-mercaptopyrimidine, 4-hydroxy-2-mercapto-6-methylpyrimidine, 4-hydroxy-2-mercapto-6-propylpyrimidine, 2-mercapto-4-methylpyrimidine, 2-mercaptopyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2-thiol, 2-mercaptoimidazole, 2-mercapto-1-methylimidazole, 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole, 3-amino- 5-Mercapto-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 3-mercapto-1H-1,2,4-triazole-3-thiol, 2-amino-5-mercapto-1,3,4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-dimercapto-1,3,4-thiadiazole, (furan-2-yl)methanethiol, 2-mercapto-5-thiazolidinone, 2-mercaptothiazoline, 2-mercapto-4(3H)-quinazolinone, 1-phenyl-1 H-tetrazole-5-thiol, 2-quinolinethiol, 2-mercapto-5-methylbenzimidazole, 2-mercapto-5-nitrobenzimidazole, 6-amino-2-mercaptobenzothiazole, 5-chloro-2-mercaptobenzothiazole, 6-ethoxy-2-mercaptobenzothiazole, 6-nitro-2-mercaptobenzothiazole, 2-mercaptonaphimidazole, 2-mercaptonaphidazole, 3-mercapto-1,2,4-triazole, 4-amino-6-mercaptopyrazolo[2,4-d]pyridine, 2-amino-6-purinethiol, 6-mercaptopurine, 4-mercapto-1H-pyrazolo[2,4-d]pyrimidine, and the like.

[0307] Examples of the compound having two or more mercapto groups in the molecule include hexanedithiol, decanedithiol, 1,4-bis(methylmercapto)benzene, butanediol bis(3-mercaptopropionate), butanediol bis(3-mercaptoacetate), ethylene glycol bis(3-mercaptoacetate), trimethylolpropane tris(3-mercaptoacetate), butanediol bis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptoacetate), trihydroxyethyl tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and 1,4-bis(3-mercaptobutyloxy)butane.

[0308] The content of the thiol compound (T) is preferably 0.5 to 50 parts by mass, more preferably 5 to 45 parts by mass, and even more preferably 10 to 40 parts by mass relative to 100 parts by mass of the polymerization initiator (D). When the content of the thiol compound (T) is within this range, sensitivity tends to be increased and developability tends to be improved.

[0309] <Leveling agent (F)>

[0310] As the leveling agent (F), there are mentioned silicone surfactants, fluorine surfactants, silicone surfactants having fluorine atoms, etc. These may have a polymerizable group in the side chain.

[0311] 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 Toray Dow Corning 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 Advanced Materials Japan Co., Ltd.).

[0312] Examples of the fluorine-based surfactant include surfactants having a fluorine-carbon chain in the molecule. Specific examples include Flourad (registered trademark) FC430, Flourad FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFACE (registered trademark) F142D, MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F177, MEGAFACE F183, MEGAFACE F554, MEGAFACE R30, MEGAFACE RS-718-K (manufactured by DIC Corporation), EFTOP (registered trademark) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), SURFLON (registered trademark) S381, SURFLON S382, SURFLON SC101, SURFLON SC105 (manufactured by AGC Corporation), and E5844 (manufactured by Daikin Fine Chemicals Laboratories).

[0313] Examples of the organosilicon-based surfactant having fluorine atoms include surfactants having a siloxane bond and a fluorocarbon chain in the molecule, and more specifically, MEGAFACE (registered trademark) R08, MEGAFACE BL20, MEGAFACE F475, MEGAFACE F477, and MEGAFACE F443 (manufactured by DIC Corporation).

[0314] When a leveling agent (F) is present, the content of the leveling agent (F) is preferably 0.0005% by mass to 1% by mass relative to the total amount of the colored curable resin composition, more preferably 0.001% by mass to 0.5% by mass, and even more preferably 0.005% by mass to 0.1% by mass. It should be noted that this content does not include the content of the pigment dispersant. If the content of the leveling agent (F) is within the aforementioned range, the flatness of the color filter can be improved.

[0315] <Other ingredients>

[0316] The colored curable resin composition may contain additives known in the art such as a filler, other polymer compounds, an adhesion promoter, a quencher, an antioxidant, a light stabilizer, and a chain transfer agent, as needed.

[0317] Examples of the adhesion promoter include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris(2-methoxyethoxy)silane, 3-glycidyloxypropyl trimethoxysilane, 3-glycidyloxypropyl methyl dimethoxysilane, 3-glycidyloxypropyl methyl diethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-chloropropyl methyl dimethoxysilane, 3-chloropropyl trimethoxysilane, 3-methacryloyloxypropyl trimethoxysilane, Silane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltriethoxysilane, etc.

[0318] <Method for producing a colored curable resin composition>

[0319] The colored curable resin composition can be prepared by mixing a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and, if necessary, a polymerization initiation aid (D1), a solvent (E), a leveling agent (F), and other components. Mixing can be performed using known or customary equipment and conditions.

[0320] The colorant (A) can be used in the form of a colorant-containing liquid, preferably by pre-mixing with a portion or all of the solvent (E) and dispersing it using a bead mill or the like until the average particle size is approximately 0.2 μm or less. In this case, the aforementioned dispersant and a portion or all of the resin (B) can be added as needed. The desired colored curable resin composition can be prepared by mixing the remaining components into the colorant-containing liquid thus obtained at predetermined concentrations.

[0321] When a dye is included as the colorant (A), the dye may be dissolved in part or all of the solvent (E) to prepare a solution, which is preferably filtered through a filter having a pore size of about 0.01 to 1 μm.

[0322] <Method for Manufacturing Color Filter>

[0323] A color filter can be formed from the colored curable resin composition of the present invention. As a method for manufacturing a colored pattern, photolithography, inkjet method, printing method, etc. can be cited. Among them, photolithography is preferred. Photolithography is a method in which the aforementioned colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithography, a colored coating film as a cured product of the aforementioned colored composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and colored coating film formed in this way are the color filter of the present invention.

[0324] The film thickness of the color filter produced is not particularly limited and can be appropriately adjusted according to the purpose, application, etc., for example, it is 30 μm or less, preferably 20 μm or less, more preferably 6 μm or less, further preferably 4.5 μm or less, preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more.

[0325] Substrates that can be used include: glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, and soda-lime glass coated with silica; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon; and substrates with thin films of aluminum, silver, or silver / copper / palladium alloys formed on the above substrates. Other color filter layers, resin layers, transistors, and circuits can also be formed on these substrates. Furthermore, silicon substrates treated with HMDS (hexamethyldisilazane) can also be used.

[0326] The formation of each color pixel by photolithography can be performed using known or customary equipment and conditions. For example, it can be produced in the following manner.

[0327] First, a colored curable resin composition is applied to a substrate and then dried under heat (prebaking) and / or reduced pressure to remove volatile components such as the solvent and dry the composition to obtain a smooth colored composition layer. Examples of coating methods include spin coating, slit coating, and slit and spin coating. The temperature during heating and drying is preferably 30°C to 120°C, more preferably 50°C to 110°C. Furthermore, the heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

[0328] When drying under reduced pressure, it is preferably performed under a pressure of 50 Pa to 150 Pa and within a temperature range of 20° C. to 25° C. The thickness of the colored composition layer is not particularly limited and can be appropriately selected depending on the desired thickness of the color filter.

[0329] Next, the colored composition layer is exposed through a photomask that forms the desired colored pattern. The pattern on the photomask is not particularly limited, and a pattern suitable for the intended application can be used. Furthermore, in order to uniformly irradiate the entire exposure surface with parallel light and accurately align the photomask with the substrate on which the colored composition layer is formed, it is preferable to use an exposure device such as a mask aligner or a stepper. When forming a colored coating film, exposure can be performed without using a photomask.

[0330] The light source used for exposure is preferably one that generates light with a wavelength of 250 nm 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 wavelengths. Specific examples include mercury lamps, light-emitting diodes, metal halide lamps, and halogen lamps.

[0331] The exposed colored composition layer is brought into contact with a developer for development, thereby forming a colored coating film (colored pattern) on the substrate. By development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. As the developer, for example, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide are preferred. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.03% by mass or more and 5% by mass or less. Furthermore, the developer may also contain a surfactant. The development method may be any of a capping immersion method, an immersion method, and a spray method. In addition, the substrate may be tilted at any angle during development.

[0332] The substrate after development is preferably washed with water.

[0333] The resulting colored pattern or colored coating film is preferably post-baked. The post-baking temperature is preferably 80°C to 250°C, more preferably 100°C to 245°C. The post-baking time is preferably 1 minute to 120 minutes, more preferably 2 minutes to 30 minutes.

[0334] The colored pattern and colored coating film obtained in this manner are useful as a color filter.

[0335] <Display Device, Solid-State Imaging Device>

[0336] The color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

[0337] Example

[0338] 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 with appropriate modifications within the scope of the gist described above and below, and all such modifications are 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."

[0339] <Preparation of Pigment Dispersion (A-1)>

[0340] The following components were mixed to obtain a pigment dispersion (A-1).

[0341]

[0342] <Preparation of Pigment Dispersion (A-2)>

[0343] The following components were mixed to obtain a pigment dispersion (A-2).

[0344]

[0345] <Preparation of Pigment Dispersion (A-3)>

[0346] The following components were mixed to obtain a pigment dispersion (A-3).

[0347]

[0348]

[0349] <Preparation of Pigment Dispersion (A-4)>

[0350] The following components were mixed to obtain a pigment dispersion (A-4).

[0351]

[0352] <Preparation of Pigment Dispersion (A-5)>

[0353] The following components were mixed to obtain a pigment dispersion (A-5).

[0354]

[0355] <Preparation of Pigment Dispersion (A-6)>

[0356] The following components were mixed to obtain a pigment dispersion (A-6).

[0357]

[0358] <Preparation of Pigment Dispersion (A-7)>

[0359] The following components were mixed to obtain a pigment dispersion (A-7).

[0360]

[0361] <Preparation of Pigment Dispersion (A-8)>

[0362] The following components were mixed to obtain a pigment dispersion (A-8).

[0363]

[0364] <Synthesis Example of Resin (B-1)>

[0365] A 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer was filled with nitrogen gas to replace the atmosphere. 256 parts of propylene glycol monomethyl ether acetate was added and heated to 80°C while stirring. Subsequently, 3,4-epoxytricyclo[5.2.1.0 2,6 ]Decan-8-yl ester or / and 3,4-epoxytricyclo[5.2.1.0 2,6 A mixed solution of 44 parts of a mixture of 9-decane esters, 57 parts of acrylic acid, 249 parts of 3-phenoxybenzyl acrylate, and 159 parts of propylene glycol monomethyl ether acetate.

[0366] Separately, a mixed solution of 25 parts 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 210 parts propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After the addition was complete, the mixture was maintained at the same temperature for 4 hours and then cooled to room temperature, yielding a copolymer having a B-type viscosity (23°C) of 51 mPa·s and a solids content of 36.0% by weight. The resulting copolymer had a weight-average molecular weight (Mw) of 11,000 and a dispersity of 1.98.

[0367] <Synthesis Example of Resin (B-2)>

[0368] To a flask equipped with a stirring apparatus, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 241 parts of propylene glycol monomethyl ether acetate were added, the mixture was stirred while nitrogen substitution was performed, and the temperature was raised to 130°C. Next, a mixture obtained by adding 34 parts of tert-butyl peroxy-2-ethylhexanoate to a monomer mixture containing 73 parts of 2-ethylhexyl acrylate, 145 parts of glycidyl methacrylate, and 10 parts of dicyclopentanyl methacrylate was added dropwise from the dropping funnel to the flask over 2 hours. After the addition was completed, the mixture was stirred for a further 30 minutes to allow for a copolymerization reaction. The flask was then purged with air, and 74 parts of acrylic acid, 1 part of triphenylphosphine, and 1 part of p-hydroxyanisole were added. The reaction was continued at 120°C for 10 hours. Subsequently, 65 parts of succinic anhydride were added to the reaction system, and the reaction was continued for a further 1.5 hours to obtain a polymer. Finally, 300 parts of propylene glycol monomethyl ether was added to the reaction solution, followed by propylene glycol monomethyl ether acetate to a polymer solids content of 40%, to obtain a polymer solution. The resulting copolymer had a viscosity of 26 mPa·s as measured by a Brookfield viscometer (23°C), a solids content of 38.5%, a weight-average molecular weight (Mw) of 6600, and an acid value (based on solids content) of 92.5 KOHmg / g.

[0369] <Synthesis Example of Resin (B-3)>

[0370] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 241 parts of propylene glycol monomethyl ether acetate were added, and the mixture was stirred while nitrogen substitution was carried out, and the temperature was raised to 130°C.

[0371] Next, 33.5 parts of t-butyl peroxy-2-ethylhexanoate was added to a monomer mixture containing 72.6 parts of 2-ethylhexyl acrylate, 145.3 parts of glycidyl methacrylate, and 9.7 parts of dicyclopentanyl methacrylate. The mixture was then added dropwise from a dropping funnel to the flask over 2 hours. After the addition was complete, the mixture was stirred for a further 30 minutes to allow for a copolymerization reaction.

[0372] The flask was then replaced with air, and 73.7 parts of acrylic acid, 0.9 parts of triphenylphosphine, and 0.9 parts of p-hydroxyanisole were added. The reaction was continued at 120°C for 10 hours. Subsequently, 65.2 parts of succinic anhydride were added to the reaction system, and the reaction was continued for a further 1.5 hours to produce a polymer. Finally, 300 parts of propylene glycol monomethyl ether were added to the reaction solution, followed by propylene glycol monomethyl ether acetate to a polymer solids concentration of 40%, to produce a polymer solution. The resulting copolymer had a weight-average molecular weight (Mw) of 6100 and an acid number (based on solids content) of 96.6 mgKOH / g.

[0373] <Synthesis Example of Resin (B-4)>

[0374] A 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer was filled with nitrogen gas to replace the atmosphere. 256 parts of propylene glycol monomethyl ether acetate was added and heated to 80°C while stirring. Subsequently, 3,4-epoxytricyclo[5.2.1.0 2,6 ]Decan-8-yl ester and 3,4-epoxytricyclo[5.2.1.0 2,6 A mixed solution of 44 parts of a mixture of 9-decane esters, 57 parts of acrylic acid, 249 parts of 3-phenoxybenzyl acrylate, and 159 parts of propylene glycol monomethyl ether acetate.

[0375] Separately, a mixed solution of 25 parts of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 210 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropwise addition, the mixture was maintained at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B-4)) having a B-type viscosity (23°C) of 51 mPa·s and a solids content of 36.0%. The resulting copolymer had a weight-average molecular weight (Mw) of 11,000 and a dispersity of 1.98.

[0376] Preparation of colored curable resin composition

[0377] <Examples 1 to 8 and Comparative Examples 1 and 2>

[0378] The components were mixed at the mixing ratios described in the table to obtain colored curable resin compositions.

[0379] [Table 1]

[0380]

[0381] <Colorant (A)>

[0382] Colorant (A-1): the aforementioned pigment dispersion (A-1)

[0383] Colorant (A-2): the aforementioned pigment dispersion (A-2)

[0384] Colorant (A-3): the aforementioned pigment dispersion (A-3)

[0385] Colorant (A-4): the aforementioned pigment dispersion (A-4)

[0386] Colorant (A-5): the aforementioned pigment dispersion (A-5)

[0387] Colorant (A-6): the aforementioned pigment dispersion (A-6)

[0388] Colorant (A-7): the aforementioned pigment dispersion (A-7)

[0389] Colorant (A-8): the aforementioned pigment dispersion (A-8)

[0390] <Resin (B)>

[0391] Resin (B-3): The above-mentioned resin (B-3) (calculated based on solid content)

[0392] Resin (B-4): The above-mentioned resin (B-4) (calculated based on solid content)

[0393] <Polymerizable Compound (C)>

[0394] Polymerizable compound (C-1): a compound represented by formula (2) (three or four Ys are acryloyl groups, X = -CH2-CH2-, a+b+c+d = 4 (each of a to f is 1), hydroxyl value = 80 mgKOH / g, a mixture of 70 mol% of ethyleneoxy-modified pentaerythritol tetraacrylate and 30 mol% of ethyleneoxy-modified pentaerythritol triacrylate)

[0395] Polymerizable compound (C-2): a compound represented by formula (4) (5 or 6 Ys are acryloyl groups, hydroxyl value = 120 mgKOH / g, a mixture of 70 mol% dipentaerythritol pentaacrylate and 30 mol% dipentaerythritol hexaacrylate)

[0396] Polymerizable compound (C-3): a compound represented by formula (3) (one, two, three, or four Ys are acryloyl groups, hydroxyl value = 280 mgKOH / g, a mixture of 5 mol% pentaerythritol monoacrylate, 30 mol% pentaerythritol diacrylate, 50 mol% pentaerythritol triacrylate, and 15 mol% pentaerythritol tetraacrylate)

[0397] Polymerizable compound (C-4): a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value = 10 mgKOH / g, alkyleneoxy group = 0)

[0398] Polymerizable compound (C-5): Ethyleneoxy-modified pentaerythritol tetraacrylate (hydroxyl value = 0 mgKOH / g, alkyleneoxy group (ethyleneoxy group) = 4)

[0399] <Polymerization Initiator (D)>

[0400] Polymerization initiator (D-1): N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine ("PBG-327 (O-acyl oxime compound)" manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.)

[0401] <Solvent (E)>

[0402] Solvent (E-1): Propylene glycol monomethyl ether acetate

[0403] Solvent (E-2): Propylene glycol monomethyl ether

[0404] <Leveling agent>

[0405] Leveling agent (F-1): Polyether-modified silicone oil (Toray Silicone SH8400, manufactured by Dow Corning Toray Co., Ltd.)

[0406] <Creation of Coloring Patterns>

[0407] The colored curable resin composition was applied to the surface of a 4-inch silicon substrate by spin coating and pre-baked at 100°C for 2 minutes to obtain a colored composition layer. After cooling, the colored composition layer was exposed to light at 500 J / m using an exposure machine (NSR-2205i11D; manufactured by Nikon Corporation). 2 ~3000J / m 2 The substrate having the colored composition layer formed thereon was irradiated with light at an exposure dose of 100 nm (based on 365 nm). During the irradiation, a photomask was used to form a dot pattern of 0.8 μm, 1.0 μm, and 2.0 μm squares (with pitches of 1.6 μm, 2.0 μm, and 4.0 μm, respectively). The irradiated colored composition layer was immersed in an aqueous developer containing 0.3% tetramethylammonium hydroxide at 23°C for 30 seconds, rinsed with water, and then post-baked on a hot plate at 220°C for 5 minutes to obtain a post-baked colored pattern.

[0408] <Residue Evaluation>

[0409] The silicon substrate having the colored pattern obtained above was observed using an electron microscope (S-4100; manufactured by Hitachi High-Tech Corporation) at a magnification of 25,000 times for the formed colored pattern and a 5 μm square unexposed portion, and evaluated according to the following criteria.

[0410] <Residue Judgment Criteria>

[0411] ◎: Residue is less than 5%

[0412] ○: Residue is 6-10%

[0413] △: Residue is 11-20%

[0414] ×: Residue is 21% or more

[0415] <Adhesion Evaluation>

[0416] In a colored pattern with a line width of 1.0 μm, 100 points (including portions peeled from the substrate) of the colored pattern at each exposure amount were observed under a microscope, the number of points remaining without peeling from the substrate was counted, and the line width of the colored pattern at an exposure amount in which 95 or more points remained was measured. The substrate adhesion of the colored pattern after post-baking was evaluated according to the following evaluation criteria.

[0417] <Adhesion Evaluation Criteria>

[0418] ◎: 0.8μm or less

[0419] ○: 0.81~0.85μm

[0420] △: 0.86~9.0μm

[0421] ×: 9.1 μm or more

[0422] It can be said that the more dots that remain at low exposure, the better the adhesion.

[0423] [Table 2]

[0424] Evaluation results Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 residue ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ × △ Adhesion ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ × ×

[0425] <Adhesion Evaluation Results>

[0426] It can be seen that Example 1 can form a color filter with reduced residue and improved adhesion compared to Comparative Examples 1 and 2. Furthermore, it can be seen that Examples 2 to 8 can also form color filters with reduced residue and improved adhesion compared to the case where conventional polymerizable compounds were used. Furthermore, Examples 1 to 8 all showed comparable reductions in residue and improved adhesion, demonstrating that polymerizable compounds having a hydroxyl value greater than 10 mgKOH / g and less than 100 mgKOH / g and having 10 or more alkyleneoxy units are suitable for use in various colorants.

Claims

1. A colored curable resin composition, characterized in that Contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), The polymerizable compound (C) includes a polymerizable compound (C1) having a hydroxyl value of 50 mgKOH / g to 100 mgKOH / g and having 2 to 8 alkyleneoxy units.

2. The colored curable resin composition according to claim 1, wherein The polymerizable compound (C1) includes a compound represented by formula (2), In the formula, Y represents a hydrogen atom or a (meth)acryloyl group, at least one Y is a (meth)acryloyl group; X represents an alkylene group having 2 to 10 carbon atoms; a to d independently represent the number of alkyleneoxy units, and a+b+c+d is 2 or more and 8 or less.

3. The colored curable resin composition according to claim 1, wherein In formula (2), the alkyleneoxy unit is represented by -CH2-CH2-O- or -CH2-CH2-CH2-O-.

4. The colored curable resin composition according to claim 1 or 2, wherein The colorant (A) is a red pigment selected from CI Pigment Red 149, 176, 177, 242, 254, 255, 264, 269, 272 and 291.

5. The colored curable resin composition according to claim 1 or 2, wherein The content of the reaction product of the (meth)acrylate compound and the secondary amine compound is 30% by mass or less based on the total of the reaction product and the polymerizable compound. 6 . A color filter formed from the colored curable resin composition according to claim 1 .

7. A display device comprising the color filter according to claim 6. 8 . A solid-state imaging device comprising the color filter according to claim 6 .

Images