Colored curable resin composition, color filter and display device

Abstract

The present invention addresses the problem of providing a colored curable resin composition capable of forming a color filter having improved pattern formability, light resistance, and solvent resistance, the pattern formability being capable of forming a good pattern shape even when the pre-baking temperature is low and the development time is prolonged. The colored curable resin composition according to the present invention is characterized by containing a colorant, a resin, a polymerizable compound and a polymerization initiator, the content of the colorant being 10-60 mass% of the total solid content of the colored curable resin composition, and the polymerization initiator comprising a compound represented by formula (X). [In formula (X), R1, R2, and R3 each independently represent an alkyl group having 1 to 17 carbon atoms, Ar represents a divalent heterocyclic group having 4 or 5 carbon atoms, and n represents 0 or 1. ]

Description

Technical Field

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

[0002] Organic EL (Electro-Luminescence) display devices using OLED (Organic Light Emitting Diode) and the like do not require a backlight and are therefore lighter and thinner than liquid crystal display devices. They can achieve high image quality such as high response speed and high contrast, are power-efficient, and can be bent, thus being used in various fields such as mobile phones, portable information terminals, and televisions.

[0003] Color filters used in organic EL display devices can be manufactured by forming a desired pattern using the following method, for example: applying a colored curable resin composition containing a colorant, a resin, a polymerizable compound, and a polymerization initiator to a substrate, drying it by heating (pre-baking) to remove volatile components such as the solvent, and drying it to obtain a smooth colored composition layer. The composition is then exposed to light through a photomask, developed, and heated (post-baking). As a polymerization initiator for forming the colored curable resin composition, for example, a compound represented by the following formula (Z) is known (Patent Document 1). Specifically, a colored curable resin composition containing this compound is pre-baked at 100°C, cured by exposure through a photomask, and developed for 60 seconds to form a color filter.

[0004]

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2022-153270 Summary of the Invention

[0008] The heat resistance of the organic light-emitting layer used in the organic EL display device is generally low, so when forming the color filter used in the organic EL display device, it is sometimes required to form a pattern at a lower temperature. In addition, in order to eliminate the developer residue, the development time is sometimes prolonged. However, the colored curable resin composition described in patent document 1 cannot be applied to a lower pre-baking temperature or a longer development time. The present inventors have conducted research and found that if the pre-baking temperature is lowered or the development time is extended, the pattern shape may be deteriorated (for example, forming an inverted cone). In addition, it is sometimes required to improve the light resistance and solvent resistance of the color filter.

[0009] Therefore, an object of the present invention is to provide a colored curable resin composition capable of forming a color filter having improved pattern formability, which refers to the ability to form a good pattern shape even at a low pre-bake temperature and a prolonged development time, and improved light resistance and solvent resistance.

[0010] The gist of the present invention is as follows.

[0011] [1] A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, and a polymerization initiator,

[0012] The content of the colorant is 10 to 60% by mass based on the total solid content of the colored curable resin composition.

[0013] The polymerization initiator includes a compound represented by formula (X).

[0014]

[0015] [In formula (X),

[0016] R 1 、R 2 and R 3 each independently represents an alkyl group having 1 to 17 carbon atoms,

[0017] Ar represents a divalent heterocyclic group having 4 or 5 carbon atoms,

[0018] n represents 0 or 1.]

[0019] [2] The colored curable resin composition according to [1], wherein the content of the compound represented by the formula (X) is 0.1 to 50 parts by mass based on 100 parts by mass of the colorant.

[0020] [3] A color filter formed from the colored curable resin composition according to [1] or [2].

[0021] [4] A display device comprising the color filter described in [3].

[0022] The colored curable resin composition of the present invention can improve at least one of pattern formability (which maintains a good pattern shape even at low pre-bake temperatures and prolonged development times), the light resistance of the resulting color filter, and the solvent resistance of the resulting color filter. Furthermore, the colored curable resin composition of the present invention preferably improves the solvent resistance of the resulting color filter, more preferably improves both the solvent resistance and light resistance of the resulting color filter, and even more preferably improves pattern formability in addition to improving the solvent resistance and light resistance of the resulting color filter. Furthermore, the colored curable resin composition of the present invention is also preferred for improving both pattern formability and the light resistance of the resulting color filter. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a schematic diagram illustrating the cross-sectional shape of a colored pattern. DETAILED DESCRIPTION

[0024] <<Colored curable resin composition>>

[0025] The colored curable resin composition of the present invention contains predetermined amounts of a colorant (hereinafter sometimes referred to as a colorant (A)), a resin (hereinafter sometimes referred to as a resin (B)), a polymerizable compound (hereinafter sometimes referred to as a polymerizable compound (C)), and a polymerization initiator (hereinafter sometimes referred to as a polymerization initiator (D)) containing a compound represented by formula (X).

[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 leveling agent (hereinafter, sometimes referred to as a leveling agent (F)).

[0029] In this specification, each component can be used alone or in combination of two or more unless otherwise specified.

[0030] Colorant (A)

[0031] Examples of the colorant (A) include dyes (hereinafter sometimes referred to as dyes (A1)) and pigments (hereinafter sometimes referred to as pigments (A2)). Among them, pigments (A2) are preferred. These may be used alone or in combination of two or more.

[0032] The dye (A1) is not particularly limited, and known dyes can be used, for example, solvent dyes, acid dyes, direct dyes, mordant dyes, etc. Examples of the dye include compounds classified as dyes in the Color Index (published by The Society of Dyers and Colourists) and known dyes described in the Dyeing Guide (published by Dyeing Co., Ltd.). In addition, based on the chemical structure, azo dyes, cyanine dyes, triarylmethane dyes, xanthene dyes, thiazole dyes, Oxazine dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, azomethine dyes, square acid Dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, phthalocyanine dyes, perylene dyes, quinophthalone dyes, isoindoline dyes, etc. Among them, azo dyes, triarylmethane dyes, xanthene dyes, and phthalocyanine dyes are preferred, and triarylmethane dyes and xanthene dyes are more preferred.

[0033] Specific examples of the dye include:

[0034] CI Solvent Yellow 4 (hereinafter, CI Solvent Yellow is omitted and only the number is recorded. The same applies to others), 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 117, 162, 163, 167, 189;

[0035] 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;

[0036] CI Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 77, 86, 99;

[0037] CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

[0038] 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;

[0039] CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35; etc. CI solvent dyes,

[0040] 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;

[0041] 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;

[0042] 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;

[0043] CI Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;

[0044] 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;

[0045] 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,

[0046] 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;

[0047] 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;

[0048] CI Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

[0049] CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

[0050] 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;

[0051] CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82; etc. CI direct dyes,

[0052] CI Disperse Yellow 51, 54, 76;

[0053] CI Disperse Violet 26, 27;

[0054] CI disperse blue 1, 14, 56, 60; etc. CI disperse dyes,

[0055] CI Basic Red 1, 9, 10;

[0056] 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;

[0057] CI Basic Violet 2;

[0058] CI basic green 1; etc. CI basic dyes,

[0059] CI Reactive Yellow 2, 76, 116;

[0060] CI Reactive Orange 16;

[0061] CI Reactive Red 36; etc. CI reactive dyes,

[0062] CI Medium Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

[0063] CI Medium Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;

[0064] CI Medium Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

[0065] CI Medium Violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58;

[0066] CI Medium Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;

[0067] 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,

[0068] CI vat green 1; etc. CI vat dyes, etc.

[0069] These dyes (A1) may be appropriately selected in accordance with the spectral spectrum of a desired color filter.

[0070] As the pigment (A2), known pigments can be used, and examples thereof include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists). In addition, examples thereof include azo pigments, cyanine pigments, triphenylmethane pigments, xanthene pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, dioxane pigments, and benzophenone pigments. Oxazine pigments, naphthoquinone pigments, quinoneimine pigments, methine pigments, azomethine pigments, squarylium pigments Pigments include acridine pigments, styryl pigments, coumarin pigments, quinoline pigments, nitro pigments, phthalocyanine pigments, perylene pigments, quinophthalone pigments, and isoindoline pigments.

[0071] Specific examples of pigments classified as pigments include:

[0072] 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, 235, 236 and other yellow pigments;

[0073] CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments;

[0074] 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, 297 and other red pigments;

[0075] CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60 and other blue pigments;

[0076] CI Pigment Violet 1, 19, 23, 29, 32, 36, 37, 38 and other purple pigments;

[0077] CI Pigment Green 7, 36, 58, 59, 62, 63, 64, 65, 66, 67 and other green pigments;

[0078] Brown pigments such as CI Pigment Brown 23 and 25;

[0079] CI Pigment Black 1, 7, 31, 32 and other black pigments, etc.

[0080] These pigments (A2) may be appropriately selected in accordance with the spectral spectrum of a desired color filter.

[0081] Among them, the pigment (A2) preferably includes phthalocyanine pigments such as CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 16, and CI Pigment Green 7, 36, 58, 59, 62, 63, 64, 65, 66, and 67. Among the above phthalocyanine pigments, at least one selected from CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and CI Pigment Green 7, 36, 58, 59, 62, 63, 64, 65, 66, and 67 is more preferable.

[0082] The content of the phthalocyanine pigment in the pigment (A2) is, for example, 20 to 100 mass %, preferably 40 to 100 mass %, more preferably 50 to 100 mass %, further preferably 80 to 100 mass %, particularly preferably 90 to 99 mass %.

[0083] Pigment (A2) can be subjected to rosin treatment, surface treatment using pigment derivatives having acidic or basic groups, grafting treatment of the pigment surface using polymer compounds, micronization treatment based on sulfuric acid micronization, cleaning treatment based on organic solvents, water, etc., removal of ionic impurities based on ion exchange methods, etc. as needed. The particle size of pigment (A2) is preferably roughly uniform. Pigment (A2) can be prepared into a pigment dispersion in a uniformly dispersed state in a solvent by dispersing the pigment containing a pigment dispersant. Pigment (A2) can be dispersed separately or a plurality of pigments can be mixed for dispersion.

[0084] As pigment dispersants, surfactants etc. can be enumerated, and can be any surfactant of cationic, anionic, nonionic and amphoteric. Specifically, surfactants such as polyester, polyamine and acrylic acid can be enumerated. These pigment dispersants can be used alone or in combination of two or more. As pigment dispersants, when 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 Chemicals (Strain) system), Disperbyk (registered trademark), BYK (registered trademark) (BYK company system) etc. can be enumerated.

[0085] When a pigment dispersant is used, its usage amount is preferably 10 to 200 parts by mass, more preferably 15 to 150 parts by mass, and even more preferably 20 to 80 parts by mass, relative to 100 parts by mass of the pigment (A2). When the usage amount of the pigment dispersant is within the above range, there is a tendency to obtain a pigment dispersion liquid in a more uniform dispersed state.

[0086] The colorant (A) preferably contains the pigment (A2). The content of the pigment (A2) in the colorant (A) is, for example, 20 to 100% by mass, preferably 50 to 100% by mass, and more preferably 80 to 100% by mass.

[0087] When a blue color filter is produced, the colorant (A) preferably contains a blue pigment, more preferably a blue phthalocyanine pigment, further preferably contains at least one blue pigment selected from CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6, and particularly preferably contains CI Pigment Blue 15:6.

[0088] When a blue color filter is produced, the colorant (A) preferably contains at least one selected from triarylmethane dyes, xanthene dyes, and violet pigments such as CI Pigment Violet 19, 23, and 37 in addition to the blue pigment.

[0089] The content of the blue pigment in the colorant (A) is, for example, 20 to 100 mass %, preferably 50 to 95 mass %, and more preferably 60 to 90 mass %.

[0090] When a red color filter is produced, the colorant (A) preferably contains a red pigment, more preferably contains at least one red pigment selected from CI Pigment Red 242, 254, 264, 269, 272, and 291, further preferably contains at least one red pigment selected from CI Pigment Red 254, 269, 272, and 291, and particularly preferably contains at least one red pigment selected from CI Pigment Red 254, 272, and 291. When a red color filter is produced, the colorant (A) also preferably contains a diketopyrrolopyrrole pigment (for example, CI Pigment Red 254, 272, and 291) as the red pigment.

[0091] When a red color filter is produced, the colorant (A) preferably contains, in addition to the red pigment, at least one selected from xanthene dyes; azo dyes; yellow pigments such as CI Pigment Yellow 139, 150, 235, and 236; and orange pigments such as CI Pigment Orange 13.

[0092] The content of the red pigment in the colorant (A) is, for example, 20 to 100 mass %, preferably 50 to 95 mass %, and more preferably 60 to 90 mass %.

[0093] When a green color filter is produced, the colorant (A) preferably contains a green pigment, more preferably contains a green phthalocyanine pigment, further preferably contains at least one green pigment selected from CI Pigment Green 7, 36, 58, 59, 62, 63, 64, 65, 66, and 67, and particularly preferably contains at least one green pigment selected from CI Pigment Green 58, 59, 62, 63, 64, 65, 66, and 67.

[0094] When a green color filter is produced, the colorant (A) preferably contains at least one selected from a phthalocyanine dye, an azo dye, and a yellow pigment such as CI Pigment Yellow 139, 150, 235, or 236 in addition to a green pigment.

[0095] The content of the green pigment in the colorant (A) is, for example, 20 to 100 mass %, preferably 50 to 95 mass %, and more preferably 60 to 90 mass %.

[0096] The content of the colorant (A) in the colored curable resin composition is 10 to 60% by mass, preferably 12 to 55% by mass, and more preferably 15 to 50% by mass, based on the total solid content. When the content of the colorant (A) is within this range, it is easier to obtain a spectrum and color density that are preferred for a color filter.

[0097] In this specification, the term "total solids content" refers to the total amount of the components obtained by excluding the solvent from the colored curable resin composition of the present invention. 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 and gas chromatography.

[0098] Resin (B)

[0099] The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6], and at least one selected from the resins [K1] to [K6] is preferred.

[0100] Resin [K1]: A copolymer comprising a structural unit derived from at least one monomer (a) selected from 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)");

[0101] Resin [K2]: A copolymer comprising a structural unit derived from the above-mentioned (a), a structural unit derived from the above-mentioned (b), and a structural unit derived from a monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter sometimes referred to as "(c)");

[0102] Resin [K3]: a copolymer comprising a structural unit derived from the above-mentioned (a) and a structural unit derived from the above-mentioned (c);

[0103] Resin [K4]: A copolymer comprising a structural unit obtained by adding the structural unit derived from the above-mentioned (b) to the structural unit derived from the above-mentioned (a) and a structural unit derived from the above-mentioned (c), and a copolymer comprising a structural unit derived from (a) to which (b) is not added;

[0104] Resin [K4′]: a copolymer comprising a structural unit obtained by adding the structural unit derived from the above-mentioned (b) to the structural unit derived from the above-mentioned (a) and a structural unit derived from the above-mentioned (c), and a copolymer containing no structural unit derived from (a) to which (b) is not added;

[0105] Resin [K5]: a copolymer comprising a structural unit obtained by adding the structural unit derived from the above-mentioned (a) and the structural unit derived from the above-mentioned (b), and a structural unit derived from the above-mentioned (c) (which may contain a structural unit derived from (b) to which (a) is not added, but preferably does not contain);

[0106] Resin [K6]: A copolymer comprising a structural unit obtained by adding the structural unit derived from the above-mentioned (b) to the above-mentioned (a) and further adding a carboxylic acid anhydride, and a structural unit derived from the above-mentioned (c).

[0107] Specific examples of (a) include: unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;

[0108] 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;

[0109] 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;

[0110] 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;

[0111] Unsaturated mono(meth)acryloyloxyalkyl) esters of divalent or higher polycarboxylic acids such as mono(2-(meth)acryloyloxyethyl) succinate and mono(2-(meth)acryloyloxyethyl) phthalate;

[0112] Unsaturated acrylic acid esters containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid.

[0113] Among them, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferred from the viewpoint of copolymerization reactivity and solubility of the resulting resin in an aqueous alkaline solution.

[0114] (b) refers to a polymerizable compound having, for example, a cyclic ether structure having 2 to 4 carbon atoms (e.g., at least one selected from an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) Preferably, the monomer has a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0115] In this specification, "(meth)acrylic acid" refers to at least one selected from acrylic acid and methacrylic acid. Expressions such as "(meth)acryloyl" and "(meth)acrylate" have the same meaning.

[0116] As (b), for example, a monomer (b1) having an oxetane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b2)"), a monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), etc. can be cited.

[0117] Examples of (b1) include monomers (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)") and monomers (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-2)").

[0118] Examples of (b1-1) include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyl)acrylate, styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, etc.

[0119] Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Corporation), compounds represented by formula (BI), and compounds represented by formula (BII).

[0120]

[0121] [In formula (BI) and formula (BII), R e and R f 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.

[0122] X e and X f Indicates a single bond, *-R g -, *-R g -O-, *-R g -S- or *-R g -NH-.

[0123] R g It represents an alkanediyl group having 1 to 6 carbon atoms.

[0124] *Indicates the bonding site with O.]

[0125] 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.

[0126] Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxy group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, and 4-hydroxybutyl.

[0127] As R e and R f , 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.

[0128] 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.

[0129] As X e and X f , preferably, a single bond, a methylene group, an ethylene group, *-CH2-O-, and *-CH2CH2-O- are mentioned, and more preferably, a single bond and *-CH2CH2-O- (* represents a bonding site with O) are mentioned.

[0130] Examples of the compound represented by formula (BI) include compounds represented by any one of formulas (BI-1) to (BI-15). Among them, compounds represented by formula (BI-1), formula (BI-3), formula (BI-5), formula (BI-7), formula (BI-9), or formulas (BI-11) to (BI-15) are preferred, and compounds represented by formula (BI-1), formula (BI-7), formula (BI-9), or formula (BI-15) are more preferred.

[0131]

[0132] Examples of the compound represented by formula (BII) include compounds represented by any one of formulas (BII-1) to (BII-15). Among them, compounds represented by formula (BII-1), formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9), or formulas (BII-11) to (BII-15) are preferred, and compounds represented by formula (BII-1), formula (BII-7), formula (BII-9), or formula (BII-15) are more preferred.

[0133]

[0134] The compound represented by formula (BI) and the compound represented by formula (BII) may be used alone or in combination of two or more. When the compound represented by formula (BI) and the compound represented by formula (BII) are used in combination, the ratio of their content [compound represented by formula (BI) : compound represented by formula (BII)] is preferably 5:95 to 95:5, more preferably 20:80 to 80:20, on a molar basis.

[0135] As (b2), a monomer having an oxetane group and a (meth)acryloyloxy group is more preferred. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, and 3-ethyl-3-acryloyloxyethyloxetane.

[0136] As (b3), a monomer having a tetrahydrofuranyl group and a (meth)acryloyloxy group is more preferred. Specific examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

[0137] As (b), (b1) is preferred in that the heat resistance, chemical resistance, etc. of the obtained color filter can be made more reliable. Moreover, (b1-2) is more preferred in that the storage stability of the colored curable resin composition is excellent.

[0138] Examples of (c) include (meth)acrylate monomers, unsaturated carboxylates such as unsaturated dicarboxylates, and vinyl monomers having an unsaturated aliphatic hydrocarbon ring, an unsaturated heterocyclic ring, or an aromatic ring.

[0139] Examples of the (meth)acrylate monomer include (meth)acrylates having a linear or branched aliphatic saturated hydrocarbon group, such as 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, and stearyl (meth)acrylate.

[0140] (Meth)acrylates having a linear or branched aliphatic unsaturated hydrocarbon group, such as allyl (meth)acrylate and propargyl (meth)acrylate;

[0141] (Meth) acrylate cyclohexyl, (meth) acrylate cyclopentyl, (meth) acrylate 2-methylcyclohexyl, (meth) acrylate tricyclo [5.2.1.0 2,6 (Meth)acrylates having a cyclic saturated hydrocarbon group, such as decane-8-yl acrylate (commonly known in the art as "dicyclopentanyl (meth)acrylate." Also, sometimes referred to as "tricyclodecyl (meth)acrylate"), isobornyl (meth)acrylate, and adamantyl (meth)acrylate;

[0142] (Meth) acrylic acid tricyclic [5.2.1.0 2,6 (Meth)acrylates having a cyclic unsaturated aliphatic hydrocarbon group, such as decen-8-yl acrylate (commonly known as "dicyclopentenyl (meth)acrylate" in this technical field) and dicyclopentyloxyethyl (meth)acrylate;

[0143] (Meth)acrylates having an aromatic ring, such as phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate, and phenoxybenzyl (meth)acrylate;

[0144] (Meth)acrylates containing a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate, and the like.

[0145] Examples of the unsaturated dicarboxylic acid ester include dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate.

[0146] Among these unsaturated carboxylic acid esters, (meth)acrylate C such as methyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferred. 1-10 alkyl esters;

[0147] (Meth) acrylic acid tricyclic [5.2.1.0 2,6 ] (Meth)acrylates having a cyclic saturated hydrocarbon group such as decan-8-yl ester;

[0148] (Meth) acrylic acid tricyclic [5.2.1.0 2,6 ] (Meth)acrylates having a cyclic unsaturated aliphatic hydrocarbon group such as decen-8-yl ester;

[0149] (Meth)acrylates having an aromatic ring, such as benzyl (meth)acrylate and phenoxybenzyl (meth)acrylate, and the like.

[0150] Examples of the vinyl monomer having an unsaturated aliphatic hydrocarbon ring include bicyclo[2.2.1]hept-2-ene (also referred to as 2-norbornene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2 .1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 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- Bicyclic unsaturated compounds such as 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.

[0151] Examples of the vinyl monomer having an unsaturated heterocyclic ring include dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide.

[0152] Examples of the vinyl monomer having an aromatic ring include styrene-based monomers such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene.

[0153] As other vinyl monomers, there can be mentioned monomers containing a nitrile group such as acrylonitrile and methacrylonitrile;

[0154] Monomers containing halogen atoms such as vinyl chloride and vinylidene chloride;

[0155] Acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

[0156] Among these vinyl monomers, preferred are styrene-based monomers such as styrene and vinyltoluene, dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide, and bicyclic unsaturated compounds such as bicyclo[2.2.1]hept-2-ene (also known as 2-norbornene), from the perspective of copolymerization reactivity and heat resistance.

[0157] The structural unit obtained by adding (b) to the structural unit derived from (a) refers to a unit formed by bonding (b) to the structural unit derived from (a) constituting the main chain of the copolymer by addition, and has a pendant unsaturated group derived from (b). In this structural unit, (a) can be any one of the above examples, and (b) can also be any one of the above examples. As (a), an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred. As (b), a monomer (b1) having an oxirane group and an ethylenically unsaturated bond is preferred, and a monomer (b1-1) having a structure in which a straight-chain or branched aliphatic unsaturated hydrocarbon is epoxidized is more preferred.

[0158] The structural unit obtained by adding (a) to the structural unit derived from (b) refers to a unit formed by bonding (a) to the structural unit derived from (b) constituting the main chain of the copolymer by addition, and has a pendant unsaturated group derived from (a). In this structural unit, (b) can be any one of the above examples, and (a) can also be any one of the above examples. As (b), preferably, it is a monomer (b1) having an oxirane group and an ethylenically unsaturated bond, and more preferably, it is a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized. As (a), preferably, it is an unsaturated monocarboxylic acid such as (meth) acrylic acid.

[0159] The structural unit obtained by adding (a) to the structural unit derived from (b) and further adding carboxylic anhydride refers to a structural unit synthesized by half-esterifying the hydroxyl group generated by the structural unit derived from (b) that is bonded to the main chain of the copolymer by addition and the carboxylic anhydride, and has a pendant carboxyl group from the carboxylic anhydride and a pendant unsaturated group from (a). In this structural unit, (b) can be any one of the above examples, and (a) can also be any one of the above examples. As (b), a monomer (b1) having an oxirane group and an ethylenically unsaturated bond is preferred, and a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is more preferred. As (a), an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred.

[0160] Examples of the carboxylic acid anhydride include saturated aliphatic polycarboxylic acid anhydrides such as malonic anhydride, succinic anhydride, glutaric anhydride, and adipic anhydride; unsaturated aliphatic polycarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, and itaconic anhydride; aromatic polycarboxylic acid anhydrides such as 3-vinylphthalic anhydride and 4-vinylphthalic anhydride; and alicyclic polycarboxylic acid anhydrides such as 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.

[0161] In the resin [K1], the ratio of the structural units derived from each monomer is preferably 2 to 60 mol% of the structural units derived from (a) and 40 to 98 mol% of the structural units derived from (b) among all the structural units constituting the resin [K1]. More preferably, the structural units derived from (a) are 10 to 50 mol% and the structural units derived from (b) are 50 to 90 mol%.

[0162] Furthermore, it is preferred that the structural unit derived from (c) is not substantially contained.

[0163] The total amount of the structural units derived from (a) and (b) in all the structural units constituting the resin [K1] is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol%.

[0164] 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.

[0165] Resin [K1] can be produced, for example, by referring to the method described in the document "Experimental Methods for Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd., Chemical Dojin, 1st edition, 1st printing, published on March 1, 1972) and the cited documents described in the document.

[0166] Specifically, the following method can be used: prescribed amounts of (a) and (b), a polymerization initiator, and a solvent are placed in a reaction vessel, and a deoxygenated atmosphere is created, for example, by replacing oxygen with nitrogen. The mixture is then heated and maintained while stirring. The polymerization initiator and solvent used herein are not particularly limited, and those commonly used in this field can be used. For example, polymerization initiators include azo compounds (such as 2,2'-azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile)) and organic peroxides (such as benzoyl peroxide and tert-butyl peroxy-2-ethylhexanoate). The solvent can be any solvent that dissolves the monomers, and examples thereof include the solvents described below as solvent (E).

[0167] The resulting copolymer may be used directly as a post-reaction solution, after concentration or dilution, or after being extracted as a solid (powder) by reprecipitation or the like. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during the polymerization, the post-reaction solution can be used directly to prepare the colored curable resin composition of the present invention, thereby simplifying the production process of the colored curable resin composition of the present invention.

[0168] In the resin [K2], the ratio of the structural units derived from each monomer is preferably 1 to 70 mol% of the structural units derived from (a), 1 to 60 mol% of the structural units derived from (b), and 20 to 95 mol% of the structural units derived from (c) in all the structural units constituting the resin [K2]. It is more preferred that the structural units derived from (a) are 3 to 50 mol%, the structural units derived from (b) are 3 to 40 mol%, and the structural units derived from (c) are 30 to 90 mol%. It is even more preferred that the structural units derived from (a) are 5 to 40 mol%, the structural units derived from (b) are 5 to 30 mol%, and the structural units derived from (c) are 40 to 80 mol%.

[0169] The total amount of the structural units derived from (a), the structural units derived from (b), and the structural units derived from (c) in all the structural units constituting the resin [K2] is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol%.

[0170] When the ratio of the structural unit 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.

[0171] In resin [K2], (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid. (b) is preferably a monomer (b1) having an oxirane group and an ethylenically unsaturated bond, and more preferably a monomer (b1-2) having an epoxidized alicyclic unsaturated hydrocarbon. (c) is preferably a (meth)acrylate having a cyclic unsaturated aliphatic hydrocarbon group, a (meth)acrylate having an aromatic ring, or a dicarbonyl imide derivative.

[0172] The resin [K2] can be produced, for example, in the same manner as described as the method for producing the resin [K1].

[0173] In the resin [K3], the ratio of the structural units derived from each monomer is preferably 2 to 70 mol% of the structural units derived from (a) and 30 to 98 mol% of the structural units derived from (c) in all the structural units constituting the resin [K3]. It is more preferred that the structural units derived from (a) are 10 to 60 mol% and the structural units derived from (c) are 40 to 90 mol%. It is even more preferred that the structural units derived from (a) are 35 to 60 mol% and the structural units derived from (c) are 40 to 65 mol%.

[0174] Furthermore, it is preferred that the structural unit derived from (b) is not substantially contained.

[0175] The total amount of the structural units derived from (a) and (c) in all the structural units constituting the resin [K3] is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol%.

[0176] Among the resins [K3], (a) unsaturated monocarboxylic acids such as (meth)acrylic acid are preferred, and (c) (meth)acrylates having an aromatic ring are preferred.

[0177] The resin [K3] can be produced, for example, in the same manner as described as the method for producing the resin [K1].

[0178] In the resin [K4], the ratio of the structural units derived from each monomer is preferably 1 to 60 mol% of the structural units derived from (a) (without addition of (b)), 1 to 50 mol% of the structural units obtained by adding the structural units derived from (a) and (b), and 30 to 90 mol% of the structural units derived from (c), more preferably 5 to 50 mol% of the structural units derived from (a) (without addition of (b)), 5 to 40 mol% of the structural units obtained by adding the structural units derived from (a) and (b), and 35 to 80 mol% of the structural units derived from (c), and even more preferably 10 to 40 mol% of the structural units derived from (a) (without addition of (b)), 10 to 25 mol% of the structural units obtained by adding the structural units derived from (a) and (b), and 40 to 75 mol% of the structural units derived from (c).

[0179] The total amount of the structural units derived from (a) (to which (b) is not added), the structural units obtained by adding the structural units derived from (a) and (b), and the structural units derived from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% of all the structural units constituting the resin [K4].

[0180] As the structural unit derived from (a) (without addition of (b)), a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred. As the structural unit obtained by adding (b) to the structural unit derived from (a), a structural unit obtained by adding a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid to a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is preferred. As the structural unit derived from (c), one or more selected from the group consisting of (meth)acrylates having a linear or branched aliphatic saturated hydrocarbon group, (meth)acrylates having a cyclic saturated hydrocarbon group, (meth)acrylates having an aromatic ring, bicyclic unsaturated compounds, and styrene-based monomers is preferred, and two or more are more preferred. When (c) contains two or more structural units derived from (c), it is preferred that two or more structural units be selected from unsaturated carboxylic acid esters such as (meth)acrylates, (meth)acrylates having a cyclic saturated hydrocarbon group, and (meth)acrylates having an aromatic ring. It is more preferred that (meth)acrylates having a cyclic saturated hydrocarbon group and (meth)acrylates having an aromatic ring be included.

[0181] Resin [K4] can be produced by obtaining a copolymer of (a) and (c), and adding a cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and / or carboxylic anhydride contained in (a).

[0182] 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 monomer is preferably the same as that exemplified for resin [K3].

[0183] Next, the cyclic ether having 2 to 4 carbon atoms contained in (b) is reacted with a portion of the carboxylic acid and / or carboxylic anhydride derived from (a) in the above copolymer.

[0184] After producing the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, (b), a reaction catalyst for a carboxylic acid or carboxylic anhydride and a cyclic ether (e.g., tris(dimethylaminomethyl)phenol, triphenylphosphine, etc.), and a polymerization inhibitor (e.g., hydroquinone, p-methoxyphenol, etc.) are placed in the flask, and the mixture is reacted at, for example, 60 to 130° C. for 1 to 20 hours to produce resin [K4].

[0185] The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 55 mol, relative to 100 mol of (a). Within this range, there is a tendency for the storage stability of the colored curable resin composition, the developability during pattern formation, and the balance between solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern to be improved.

[0186] The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b), and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b), and (c).

[0187] The reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the calorific value based on the polymerization, etc. In addition, the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the calorific value based on the polymerization, etc., similarly to the polymerization conditions.

[0188] In the resin [K4'], the ratio of the structural units derived from the respective monomers is preferably 5 to 95 mol% of the structural units derived from the structural units (a) and (b) added together, and 5 to 95 mol% of the structural units derived from (c) among all the structural units constituting the resin [K4']. More preferably, the structural units derived from the structural units (a) and (b) added together are 15 to 90 mol% and 10 to 85 mol% of the structural units derived from (c). Even more preferably, the structural units derived from the structural units (a) and (b) added together are 20 to 80 mol% and 20 to 80 mol% of the structural units derived from (c).

[0189] Furthermore, the structural unit derived from (a) to which (b) is not added is substantially not contained.

[0190] The total amount of the structural units derived from the addition of the structural units derived from (a) and (b) and the structural units derived from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% of all the structural units constituting the resin [K4′].

[0191] The structural unit obtained by adding the structural unit derived from (a) to (b) is preferably a structural unit obtained by adding a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid to a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized. The structural unit derived from (c) is preferably one or more selected from (meth)acrylates having a linear or branched aliphatic saturated hydrocarbon group and (meth)acrylates having a cyclic saturated hydrocarbon group, and more preferably two or more selected from the group consisting of.

[0192] The resin [K4'] can be produced by referring to the method for producing the resin [K4] described above, and the amount of (b) used is preferably 100 mol relative to 100 mol of (a).

[0193] In the resin [K5], the ratio of the structural units derived from each monomer is, among all the structural units constituting the resin [K5], 0 to 30 mol% of the structural units derived from (b) (without addition of (a)), 5 to 95 mol% of the structural units obtained by adding the structural units derived from (b) and (a), and 5 to 95 mol% of the structural units derived from (c). More preferably, 0 to 10 mol% of the structural units derived from (b) (without addition of (a)), 15 to 90 mol% of the structural units obtained by adding the structural units derived from (b) and (a), and 10 to 85 mol% of the structural units derived from (c). Even more preferably, 0 to 5 mol% of the structural units derived from (b) (without addition of (a)), 20 to 80 mol% of the structural units obtained by adding the structural units derived from (b) and (a), and 20 to 80 mol% of the structural units derived from (c).

[0194] The total amount of the structural units derived from (b) (to which (a) is not added), the structural units obtained by adding the structural units derived from (b) and (a), and the structural units derived from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% in all the structural units constituting the resin [K5].

[0195] As the structural unit derived from (b) (to which (a) is not added), a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is preferred. As the structural unit obtained by adding the structural unit derived from (b) to (a), a structural unit obtained by adding the structural unit derived from the monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized to an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred. As the structural unit derived from (c), one or more selected from (meth)acrylates having a linear or branched aliphatic saturated hydrocarbon group and (meth)acrylates having a cyclic saturated hydrocarbon group are preferred, and two or more selected from the group consisting of are preferred.

[0196] Resin [K5] is subjected to the same method for producing resin [K1] as described above as a first step to obtain a copolymer of (b) and (c). As described above, the obtained copolymer may be used directly as a solution after the reaction, after concentration or dilution, or after being extracted as a solid (powder) by methods such as reprecipitation.

[0197] The ratio of the structural units derived from (b) and (c) relative to the total molar number of all structural units constituting the above-mentioned copolymer is preferably 5 to 95 mol% for the structural units derived from (b) and 5 to 95 mol% for the structural units derived from (c), and more preferably 10 to 90 mol% for the structural units derived from (b) and 10 to 90 mol% for the structural units derived from (c).

[0198] Furthermore, resin [K5] can be obtained by reacting the cyclic ether derived from (b) contained in the copolymer of (b) and (c) with the carboxylic acid or carboxylic anhydride contained in (a) under the same conditions as those for producing resin [K4] or resin [K4′].

[0199] The amount of (a) reacted with the copolymer is preferably 5 to 100 mol per 100 mol of (b). Since cyclic ethers have high reactivity and are less likely to leave unreacted (b), (b1) is preferred as (b) for use in the resin [K5], and (b1-1) is more preferred.

[0200] In the resin [K6], the ratio of the structural units derived from each monomer is preferably 0 to 30 mol% of the structural units derived from (b) (without addition of (a)), 20 to 85 mol% of the structural units obtained by adding the structural units derived from (b) to (a) (without addition of carboxylic acid anhydride), 2 to 40 mol% of the structural units obtained by adding the structural units derived from (b) to (a) and further adding carboxylic acid anhydride, and 10 to 60 mol% of the structural units derived from (c), and more preferably 0 to 10 mol% of the structural units derived from (b) (without addition of (a)), and 20 to 85 mol% of the structural units obtained by adding the structural units derived from (b) to (a). The content of the structural units derived from (b) (without addition of carboxylic anhydride) is 40 to 80 mol%, the content of the structural units derived from (b) and (a) and further addition of carboxylic anhydride is 3 to 30 mol%, and the content of the structural units derived from (c) is 15 to 50 mol%. More preferably, the content of the structural units derived from (b) (without addition of (a)) is 0 to 5 mol%, the content of the structural units derived from (b) and (a) (without addition of carboxylic anhydride) is 50 to 70 mol%, the content of the structural units derived from (b) and (a) and further addition of carboxylic anhydride is 5 to 20 mol%, and the content of the structural units derived from (c) is 20 to 40 mol%.

[0201] The total amount of the structural units derived from (b) (to which (a) is not added), the structural units obtained by adding the structural units derived from (b) and (a) (to which carboxylic anhydride is not added), the structural units obtained by adding the structural units derived from (b) and (a) and further adding carboxylic anhydride, and the structural units derived from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% in all the structural units constituting the resin [K6].

[0202] As the structural unit derived from (b) (without addition of (a)), a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is preferred. As the structural unit obtained by adding (a) to the structural unit derived from (b) (without addition of carboxylic anhydride), a structural unit obtained by adding an unsaturated monocarboxylic acid such as (meth)acrylic acid to the structural unit derived from (b) (without addition of carboxylic anhydride) is preferred. As the structural unit obtained by adding (a) to the structural unit derived from (b) and further adding a carboxylic anhydride, a structural unit obtained by adding an unsaturated monocarboxylic acid such as (meth)acrylic acid to the structural unit derived from (b) (without addition of carboxylic anhydride) is preferred. The structural unit derived from (c) is preferably one or more selected from (meth)acrylates having a linear or branched aliphatic saturated hydrocarbon group and (meth)acrylates having a cyclic saturated hydrocarbon group, and more preferably two or more selected from (meth)acrylates.

[0203] Resin [K6] is subjected to the same method for producing resin [K1] as described above as a first step to obtain a copolymer of (b) and (c). As described above, the obtained copolymer may be used directly as a solution after the reaction, after concentration or dilution, or after being extracted as a solid (powder) by methods such as reprecipitation.

[0204] The ratio of the structural units derived from (b) and (c) relative to the total molar number of all structural units constituting the above-mentioned copolymer is preferably 5 to 95 mol% for the structural units derived from (b) and 5 to 95 mol% for the structural units derived from (c), and more preferably 10 to 90 mol% for the structural units derived from (b) and 10 to 90 mol% for the structural units derived from (c).

[0205] Furthermore, under the same conditions as those for the production of resin [K4], the cyclic ether derived from (b) in the copolymer of (b) and (c) is reacted with the carboxylic acid or carboxylic anhydride in (a). The amount of (a) used is preferably 80 to 100 mol per 100 mol of (b).

[0206] The hydroxyl group generated by the reaction of the cyclic ether with the carboxylic acid or carboxylic anhydride contained in (a) reacts with the carboxylic anhydride. The amount of the carboxylic anhydride used is preferably 0.05 to 1 mol, more preferably 0.10 to 0.8 mol, and even more preferably 0.13 to 0.7 mol per 1 mol of (a) used (in other words, per 1 mol of hydroxyl group generated by using (a)).

[0207] Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] Decyl ester / (meth)acrylic acid copolymer and other resins [K1];

[0208] 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, 3,4-epoxytricyclo[5.2.1.0 2,6 ]Decanol / (meth)acrylate / N-cyclohexylmaleimide / (meth)acrylate tricyclic[5.2.1.0 2,6 ]Decenyl-8-yl ester copolymer, acrylic acid 3,4-epoxy tricyclic [5.2.1.0 2,6 ]Decyl ester / (meth)acrylic acid / benzyl (meth)acrylate copolymer, 3,4-epoxytricyclo[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];

[0209] Resins such as benzyl (meth)acrylate / (meth)acrylic acid copolymer and styrene / (meth)acrylic acid copolymer [K3];

[0210] Resins obtained by adding glycidyl (meth)acrylate to a portion of the carboxylic acid groups of a benzyl (meth)acrylate / (meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to a portion of the carboxylic acid groups of a benzyl (meth)acrylate / dicyclopentanyl (meth)acrylate / (meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to a portion of the carboxylic acid groups of a tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to a portion of the carboxylic acid groups of a tricyclodecyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to a portion of the carboxylic acid groups of a norbornene / vinyltoluene / (meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to a portion of the carboxylic acid groups of a norbornene / styrene / (meth)acrylic acid copolymer, and the like [K4];

[0211] Resins such as a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate / (meth)acrylic acid with glycidyl (meth)acrylate, and a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid with glycidyl (meth)acrylate [K4'];

[0212] 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];

[0213] 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 / tricyclodecyl (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 methyl (meth)acrylate / 2-ethylhexyl (meth)acrylate / tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate with (meth)acrylic acid and further reacting it with succinic anhydride [K6], etc.

[0214] The resin (B) is preferably at least one selected from the group consisting of the resin [K1], the resin [K2], and the resin [K4], and more preferably the resin [K4].

[0215] The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. When the molecular weight is within this range, the hardness of the color filter is improved, the residual film rate is high, the solubility of the unexposed portion in the developer is good, and the resolution of the colored pattern tends to be improved.

[0216] 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.

[0217] The acid value of 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 on a solids basis. The acid value is measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin (B) and can be determined, for example, by titration with an aqueous potassium hydroxide solution.

[0218] The content of the resin (B) is preferably 2 to 70% by mass, more preferably 10 to 65% by mass, and even more preferably 30 to 60% by mass, based on the total solid content of the colored curable resin composition. When the content of the resin (B) is within this range, a colored pattern can be formed, and the resolution and residual film rate of the colored pattern tend to be improved.

[0219] <Polymerizable compound (C)>

[0220] 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.

[0221] Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-ethylhexyl carbitol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-vinyl pyrrolidone, and the above-mentioned monomers (a), (b), and (c).

[0222] Examples of the polymerizable compound having two ethylenically unsaturated bonds include glycerol di(meth)acrylate, 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.

[0223] The polymerizable compound (C) is particularly preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol poly(meth)acrylate (e.g., pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate), dipentaerythritol poly(meth)acrylate (e.g., dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate), tripentaerythritol poly(meth)acrylate (e.g., tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate), pentaerythritol poly(meth)acrylate (e.g., pentaerythritol deca(meth)acrylate, pentaerythritol nona(meth)acrylate), tris(2-(meth)acryloyloxyethyl)isocyanurate, alkoxylated pentaerythritol poly(meth)acrylate (e.g., ethoxylated pentaerythritol), and hydroxylated ... tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate), alkoxylated dipentaerythritol multi(meth)acrylate (e.g., ethoxylated dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol penta(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate), caprolactone-modified pentaerythritol multi(meth)acrylate (e.g., caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate), caprolactone-modified dipentaerythritol multi(meth)acrylate (e.g., caprolactone-modified dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate), and the like.

[0224] Among them, it is preferred that at least one selected from glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and dipentaerythritol poly(meth)acrylate be contained, and it is more preferred that at least one selected from glycerol triacrylate, trimethylolpropane triacrylate, and dipentaerythritol polyacrylate be contained.

[0225] The weight average molecular weight of the polymerizable compound (C) is preferably 50 to 4,000, more preferably 70 to 3,500, further preferably 100 to 3,000, further preferably 150 to 2,900, and particularly preferably 250 to 1,500.

[0226] The content of the polymerizable compound (C) is, for example, 1 to 80 mass %, preferably 5 to 50 mass %, and more preferably 10 to 30 mass % in the total amount of the solid content of the colored curable resin composition.

[0227] <Polymerization initiator (D)>

[0228] The polymerization initiator (D) includes a compound represented by formula (X) (hereinafter sometimes referred to as compound (X)). In the production of the color filter, it is believed that the residue of the polymerization initiator after releasing active substances such as active free radicals and acids, and unreacted polymerization initiator remain in the film, and the residue of the polymerization initiator, etc., are unstable to light and are colored, and there is a situation in which the color of the color filter after light irradiation is caused to change. It is believed that since the residue of compound (X), etc. is not easily colored by light irradiation, the color change of the color filter after light irradiation can be suppressed in the present invention, that is, the light resistance of the color filter obtained is excellent. In addition, by including compound (X) in the colored curable resin composition, even if the pre-bake temperature is reduced and the development time is extended (i.e., regardless of the manufacturing conditions of the color filter), a good pattern shape can be formed. In addition, by including compound (X) in the colored curable resin composition, the solvent resistance of the obtained color filter can be improved.

[0229]

[0230] [In formula (X),

[0231] R 1 、R 2 and R 3 each independently represents an alkyl group having 1 to 17 carbon atoms,

[0232] Ar represents a divalent heterocyclic group having 4 or 5 carbon atoms,

[0233] n represents 0 or 1.]

[0234] As R 1 、R 2 and R 3 Examples of the alkyl group represented by include:

[0235] Straight-chain alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl and n-heptadecyl;

[0236] Isopropyl, isobutyl, sec-butyl, tert-butyl, 2-ethylbutyl, 3,3-dimethylbutyl, 1,1,3,3-tetramethylbutyl, 1-methylbutyl, 1-ethylpropyl, 3-methylbutyl, neopentyl, 1,1-dimethylpropyl, 1,1,2-trimethylpropyl, 2-methylpentyl, 3-ethylpentyl, 1,3-dimethylbutyl, 2-propylpentyl, 1-ethyl-1,2-dimethylpropyl, 1-methylpentyl, 4 branched-chain alkyl groups such as 1-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2-ethylhexyl, 1-methylhexyl, 1-ethylpentyl, 1-propylbutyl, 3-ethylheptyl, 2,2-dimethylheptyl, 1-methylheptyl, 1-ethylhexyl, 1-propylpentyl, 1-methyloctyl, 1-ethylheptyl, 1-propylhexyl, 1-butylpentyl, 1-methylnonyl, 1-ethyloctyl, 1-propylheptyl and 1-butylhexyl.

[0237] In formula (X), two R 1 The two R 2 The two R 3 They may be the same or different, but are preferably the same.

[0238] The above R 1 An alkyl group having 1 to 12 carbon atoms is preferred, an alkyl group having 2 to 8 carbon atoms is more preferred, an alkyl group having 2 to 4 carbon atoms is further preferred, and an ethyl group is particularly preferred.

[0239] The above R 2 An alkyl group having 1 to 12 carbon atoms is preferred, an alkyl group having 1 to 8 carbon atoms is more preferred, an alkyl group having 1 to 4 carbon atoms is further preferred, and a methyl group is particularly preferred.

[0240] The above R 3 An alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 4 carbon atoms is more preferred, and a methyl group is further preferred.

[0241] The divalent heterocyclic group having 4 or 5 carbon atoms represented by Ar means a group in which two hydrogen atoms directly bonded to atoms constituting the ring in the heterocyclic ring having 4 or 5 carbon atoms are substituted as bonding sites.

[0242] The heterocyclic ring constituting the above-mentioned divalent heterocyclic group may be a heterocyclic ring having aromaticity (i.e., an aromatic heterocyclic ring) or a heterocyclic ring not having aromaticity (i.e., a non-aromatic heterocyclic ring), and is preferably an aromatic heterocyclic ring. Specific examples of the heterocyclic ring constituting the above-mentioned divalent heterocyclic group include a furan ring, a pyrrole ring, a thiophene ring, a 1,2,3-triazole ring, an imidazole ring, a pyrazole ring, a thiazole ring, five-membered aromatic heterocycles such as azole ring; six-membered aromatic heterocycles such as pyrazine ring, pyrimidine ring, pyridazine ring, 1,3,5-triazine ring, etc.

[0243] In formula (X), two Ar's may be the same or different, but are preferably the same.

[0244] The above-mentioned Ar is preferably a group in which two hydrogen atoms directly bonded to atoms constituting the ring in an aromatic heterocyclic ring having 4 or 5 carbon atoms are substituted as a bonding site, more preferably a group in which two hydrogen atoms directly bonded to atoms constituting the ring in a five-membered aromatic heterocyclic ring are substituted as a bonding site, further preferably a group in which two hydrogen atoms directly bonded to atoms constituting the ring in a furan ring or a thiophene ring are substituted as a bonding site, and particularly preferably a group in which two hydrogen atoms directly bonded to atoms constituting the ring in a thiophene ring are substituted as a bonding site.

[0245] n represents 0 or 1, and is preferably 0. In formula (X), two n's may be the same or different, and are preferably the same.

[0246] Specific examples of the compound (X) include compounds (X-1) to (X-48) shown in Table 1.

[0247] [Table 1]

[0248]

[0249] In Table 1, ar-1 represents a group represented by the following formula (ar-1), and ar-2 represents a group represented by the following formula (ar-2). In the following formulae, * represents a bonding site.

[0250]

[0251] In the polymerization initiator (D), the content of the compound (X) is, for example, 10 to 100% by mass, preferably 20 to 100% by mass. The lower limit of the above-mentioned content may be 30% by mass or more, 50% by mass or more, or 80% by mass or more. In addition, from the viewpoint of making the obtained color filter particularly excellent in light resistance, the content of the compound (X) in the polymerization initiator (D) is preferably 10 to 100% by mass, more preferably 20 to 60% by mass, and even more preferably 20 to 40% by mass.

[0252] The content of the compound (X) is preferably 0.1 to 50 parts by mass, more preferably 1 to 40 parts by mass, further preferably 1 to 35 parts by mass, and particularly preferably 3 to 25 parts by mass, relative to 100 parts by mass of the colorant (A).

[0253] The content of the compound (X) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 2 to 10 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C).

[0254] The polymerization initiator (D) may contain a polymerization initiator other than the compound (X) (hereinafter sometimes referred to as other polymerization initiator). The other polymerization initiator may be any compound other than the compound (X) as long as it generates active radicals, acids, etc. under the action of light or heat to initiate polymerization.

[0255] Examples of other polymerization initiators include O-acyl oxime compounds other than compound (X), alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.

[0256] The O-acyl oxime compound is a compound having a partial structure represented by formula (d-1).

[0257] Wherein, * represents the bonding site.

[0258]

[0259] Examples of the O-acyl oxime compounds 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-dioxolanemethoxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-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-acetoxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine, etc. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02, OXE03 (all manufactured by BASF), ADEKA ARKLS (registered trademark) N-1919, NCI-730, NCI-831, NCI-930 (all manufactured by ADEKA), and TR-PBG327 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) can also be used.

[0260] 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 bonding site.

[0261]

[0262] Examples of the compound having a partial structure represented by formula (d-2) include 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]butan-1-one. Commercially available products such as Irgacure (registered trademark) 369, 907, and 379 (all manufactured by BASF) can also be used.

[0263] 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 benzyl dimethyl ketal.

[0264] In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (d-2).

[0265] 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.

[0266] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) can also be used.

[0267] 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'-tetraphenylbiimidazole, and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole. Biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboalkoxy groups (e.g., see JP-A-48-38403 and JP-A-62-174204), and the like. Among them, compounds represented by the following formulas and mixtures thereof are preferred.

[0268]

[0269] Other polymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl benzoylformate, and titanocene compounds. These are preferably used in combination with the polymerization initiator aid (D1) (particularly amine compounds) described below.

[0270] In addition, other polymerization initiators include polymerization initiators that generate acid, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl iodide, p-Toluenesulfonate, diphenyliodonium Hexafluoroantimonate, etc. Salts, nitrobenzyl tosylate, benzoin tosylate, etc.

[0271] The other polymerization initiator is preferably at least one selected from alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and biimidazole compounds, more preferably O-acyloxime compounds and / or biimidazole compounds, and still more preferably O-acyloxime compounds.

[0272] When other polymerization initiators are used, the content thereof is preferably 10 to 500 parts by mass, more preferably 20 to 400 parts by mass, and even more preferably 50 to 250 parts by mass, relative to 100 parts by mass of compound (X).

[0273] The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 2 to 10 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, there is a tendency for increased sensitivity and shortened exposure time, thereby improving the productivity of the color filter.

[0274] <Polymerization initiator aid (D1)>

[0275] The polymerization initiation aid (D1) is a compound or a sensitizer for accelerating the polymerization of the polymerizable compound (C) initiated by the polymerization initiator (D).

[0276] Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

[0277] 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.) may also be used.

[0278] 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.

[0279] Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0280] 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, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

[0281] When using these polymerization initiation aids (D1), the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 2 to 10 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.

[0282] Solvent (E)

[0283] The solvent (E) is not particularly limited, and any solvent commonly used in this field can be used.

[0284] Examples of the solvent (E) include ester solvents (solvents containing -COO- and not -O- in the molecule), ether solvents (solvents containing -O- and not -COO- in the molecule), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and not -COO- in the molecule), alcohol solvents (solvents containing -OH and not -O-, -CO-, and -COO- in the molecule), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide. Two or more of these solvents may be used in combination.

[0285] 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.

[0286] Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dimethoxy-1-butanol, 3-methoxy-3-methylbutanol ... Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether and methyl anisole, etc.

[0287] 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.

[0288] 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.

[0289] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0290] Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

[0291] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0292] Among the above solvents, organic solvents having a boiling point of 120°C to 180°C at 1 atm are preferred from the perspectives of coating and drying properties. The organic solvent is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, and N,N-dimethylformamide. More preferably, the organic solvent is at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethyl lactate, and ethyl 3-ethoxypropionate.

[0293] When a solvent (E) is present, the content of the solvent (E) is generally 99.99% by mass or less, preferably 40 to 99% by mass, more preferably 50 to 97% by mass, further preferably 70 to 96% by mass, and even more preferably 73 to 95% by mass, relative to the total amount of the colored curable resin composition. In other words, the total amount of solids in the colored curable resin composition is generally 0.01% by mass or more, preferably 1 to 60% by mass, more preferably 3 to 50% by mass, further preferably 4 to 30% by mass, and even more preferably 5 to 27% by mass. When the content of the solvent (E) is within this range, the flatness during coating is improved, and when a color filter is formed, the color density is not insufficient, thereby tending to improve display properties.

[0294] <Leveling agent (F)>

[0295] Examples of the leveling agent (F) include silicone surfactants, fluorine-based surfactants, and silicone surfactants having fluorine atoms, etc. These may have a polymerizable group in a side chain.

[0296] Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule, including polyether-modified silicone oils. 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 name: manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.).

[0297] Examples of fluorine-based surfactants include surfactants having a fluorine carbon chain in the molecule. Specific examples include FLUORAD (registered trademark) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by AGC Corporation) and E5844 (manufactured by Daikin Fine Chemicals Laboratories, Ltd.), etc.

[0298] 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, MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, and MEGAFAC F443 (manufactured by DIC Corporation).

[0299] When a leveling agent (F) is included, the content of the leveling agent (F) is preferably 0.0005 to 1% by mass, more preferably 0.001 to 0.5% by mass, and even more preferably 0.005 to 0.1% by mass relative to the total amount of the colored curable resin composition. This content does not include the content of the pigment dispersant. When the content of the leveling agent (F) is within this range, the flatness of the color filter can be improved.

[0300] <Other ingredients>

[0301] The colored curable resin composition of the present invention 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.

[0302] <Method for producing a colored curable resin composition>

[0303] The colored curable resin composition of the present invention 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.

[0304] When using pigment (A2) as colorant (A), it can be pre-mixed with part or all of solvent (E) and dispersed using a bead mill or the like to an average particle size of about 0.2 μm or less, and then used as a pigment dispersion. Preferably, it is used as a pigment dispersion. In this case, part or all of the above-mentioned pigment dispersant and resin (B) can be added as needed. The desired colored curable resin composition can be prepared by mixing the remaining components into the thus-obtained pigment dispersion to achieve a predetermined concentration.

[0305] When a dye is used as the colorant (A), the dye may be dissolved in part or all of the solvent (E) to prepare a solution for use in preparing the colored curable resin composition. The solution is preferably filtered using a filter having a pore size of about 0.01 to 1 μm.

[0306] Color Filters

[0307] As a method for producing a color pattern of a color filter using the colored curable resin composition of the present invention, photolithography, inkjet method, printing method, etc. can be mentioned. Among them, photolithography is preferred. Photolithography is a method in which the above-mentioned colored curable resin composition is applied to a substrate and dried to form a composition layer, and the composition layer is exposed through a photomask and developed. In the photolithography method, by not using a photomask and / or not developing during exposure, a colored coating film as a cured product of the above-mentioned composition layer can be formed.

[0308] The film thickness of the color filter (cured film) is, for example, 30 μm or less, preferably 20 μm or less, more preferably 6 μm or less, further preferably 3 μm or less, and can be 1.5 μm or less or 0.5 μm or less. In addition, it is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more.

[0309] As substrates, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda-lime glass coated with silicon dioxide, resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, silicon, and substrates having thin films of aluminum, silver, or silver / copper / palladium alloys formed thereon can be used. Other color filter layers, resin layers, transistors, circuits, and the like can be formed on these substrates. Alternatively, silicon substrates treated with HMDS can be used.

[0310] The formation of each color pixel based on the photolithography method can be carried out using a known or customary device and conditions. For example, it can be produced as described below. First, the colored curable resin composition is applied to the substrate, and heat-dried (pre-baked) and / or dried under reduced pressure to remove the solvent and other volatilized substances and dry them to obtain a smooth composition layer. As coating methods, spin coating, slit coating, slit and spin coating, etc. can be mentioned.

[0311] The temperature during heat drying (pre-baking temperature) is preferably 30 to 120°C, more preferably 50 to 110°C. When pattern formation is performed at a low temperature, there is generally a tendency for the pre-baking temperature to be lower. When the pre-baking temperature is low (e.g., 30 to 90°C), solvent tends to remain in the composition layer. In the development described later, not only the unexposed portion but also the bottom of the exposed portion tends to dissolve, resulting in poor pattern shape and peeling. However, according to the colored curable resin composition of the present invention, even when the pre-baking temperature is a lower temperature (e.g., 30 to 90°C, preferably 50 to 90°C) required in the manufacture of organic EL display devices, a colored pattern with a good shape can be formed, and thus it is preferred.

[0312] The heating time (prebaking time) is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

[0313] When drying under reduced pressure is performed, it is preferably performed under a pressure of 50 to 150 Pa and a temperature range of 20 to 25°C.

[0314] The film thickness of the composition layer is not particularly limited and may be appropriately selected depending on the film thickness of the target color filter.

[0315] Next, the composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the target application can be used. As the light source used in the exposure, a light source that generates light with a wavelength of 250 to 450 nm is preferably used. For example, light less than 250 nm can be cut off using a filter that cuts off this wavelength region, or light near 436 nm, near 408 nm, and near 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength regions. Specifically, mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, etc. can be cited. In order to be able to evenly irradiate parallel light to the entire exposure surface and accurately align the photomask with the substrate, it is preferred to use a reduced projection exposure device or a close-type exposure device such as a mask aligner and a stepper.

[0316] The exposed composition layer is brought into contact with a developer for development, thereby forming a colored pattern on the substrate. The unexposed portion of the composition layer is dissolved in the developer by development 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 to 10% by mass, more preferably 0.03 to 5% by mass. In addition, the developer may contain a surfactant. The development method may be any one of a paddle method, an immersion method, and a spray method. Furthermore, the substrate is tilted at any angle during development. The development time is not particularly limited, but is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, further preferably 30 seconds to 2 minutes, and particularly preferably 70 seconds to 2 minutes.

[0317] After development, water washing is preferably performed.

[0318] The obtained colored pattern is preferably further post-baked. The post-baking temperature may be 200°C or less, preferably 170°C or less, and more preferably 150°C or less. When forming a color filter used in an organic EL display device, it is preferably post-baked at a lower temperature (for example, 130°C or less, preferably 100°C or less, and more preferably 90°C or less). The lower limit of the post-baking temperature is preferably 30°C or more, and more preferably 50°C or more. The post-baking time is preferably 1 to 120 minutes, and more preferably 5 to 60 minutes.

[0319] The colored pattern and colored coating film thus obtained are useful as a color filter, and the color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, etc.), electronic paper, solid-state imaging devices, and the like.

[0320] Example

[0321] The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the Examples, % and parts indicating the content or amount used are by mass unless otherwise specified.

[0322] <Pigment Dispersion Preparation Example 1: Preparation of Pigment Dispersion (A-1)>

[0323] 14.1 parts of CI Pigment Blue 15:6, 0.5 parts of CI Pigment Violet 23, 4.0 parts of an acrylic pigment dispersant, and 81 parts of propylene glycol monomethyl ether acetate were mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A-1).

[0324] <Pigment Dispersion Preparation Example 2: Preparation of Pigment Dispersion (A-2)>

[0325] 7.2 parts of CI Pigment Green 36, 0.8 parts of CI Pigment Yellow 139, 7.0 parts of CI Pigment Yellow 150, 4.0 parts of acrylic pigment dispersant, and 81 parts of propylene glycol monomethyl ether acetate were mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A-2).

[0326] <Pigment Dispersion Preparation Example 3: Preparation of Pigment Dispersion (A-3)>

[0327] 7.8 parts of CI Pigment Red 291, 6.2 parts of CI Pigment Red 269, 1.1 parts of CI Pigment Yellow 139, 4.0 parts of acrylic pigment dispersant, and 81 parts of propylene glycol monomethyl ether acetate were mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A-3).

[0328] <Resin Synthesis Example 1: Preparation of Resin (B-1)>

[0329] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 349 parts of propylene glycol monomethyl ether acetate were added, and the temperature was raised to 120° C. while stirring and nitrogen substitution was carried out.

[0330] Next, a mixture consisting of 169.2 parts of benzyl methacrylate, 103.3 parts of methacrylic acid, and 52.9 parts of dicyclopentanyl methacrylate, to which 23.4 parts of t-butyl peroxy-2-ethylhexanoate had been added, was added dropwise to the flask using a dropping funnel over 2 hours. After the addition was complete, the mixture was stirred for a further 30 minutes to allow for a copolymerization reaction.

[0331] The flask was then purged with air, and 51.2 parts of glycidyl methacrylate, 1.1 parts of triphenylphosphine, and 1.1 parts of p-methoxyphenol were added. The reaction was continued at 120°C for 10 hours to produce a polymer (resin (B-1)). Finally, propylene glycol monomethyl ether acetate was added to the reaction solution to a polymer solids concentration of 40%, yielding a resin solution. The weight-average molecular weight of resin (B-1) contained in this resin solution was 10,300, and the acid value per unit solids of resin (B-1) was 120.9 mg-KOH / g.

[0332] The polystyrene-equivalent weight average molecular weight (Mw) of the resin was measured by GPC under the following conditions.

[0333] Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)

[0334] Column:TSK-GELG2000HXL

[0335] Column temperature: 40℃

[0336] Solvent: Tetrahydrofuran

[0337] Flow rate: 1.0 mL / min

[0338] Solid content concentration of analysis sample: 0.001 to 0.01 mass%

[0339] Injection volume: 50 μL

[0340] Detector: RI

[0341] Calibration standard substances: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

[0342] <Examples 1 to 7 and Comparative Examples 1 and 2>

[0343] (1) Preparation of colored curable resin composition

[0344] A pigment dispersion, resin solution, polymerizable compound, polymerization initiator, leveling agent, and solvent were mixed to obtain the composition shown in Table 2 to obtain a colored curable resin composition. The solvent was mixed to achieve a solids content of 18% in the colored curable resin composition. The amounts of each component in Table 2 are expressed in parts.

[0345] [Table 2]

[0346]

[0347] In Table 2, the components are as follows.

[0348] Colorant (A-1): CI Pigment Blue 15:6 and CI Pigment Violet 23

[0349] Colorant (A-2): CI Pigment Green 36, CI Pigment Yellow 139 and CI Pigment Yellow 150

[0350] Colorant (A-3): CI Pigment Red 291, CI Pigment Red 269 and CI Pigment Yellow 139

[0351] Resin (B-1): Resin (B-1) (solid content conversion)

[0352] Polymerizable compound (C-1): Glyceryl triacrylate (ARONIX (registered trademark) M-930; manufactured by Toagosei Co., Ltd.)

[0353] Polymerization initiator (D-1): a compound represented by the following formula (X-1)

[0354]

[0355] Polymerization initiator (D-2): ADEKA ARKLS (registered trademark) NCI-831E (manufactured by ADEKA Corporation), a compound represented by the following formula (Z)

[0356]

[0357] Polymerization initiator (D-3): ADEKA ARKLS (registered trademark) NCI-730 (manufactured by ADEKA Corporation)

[0358] Leveling agent (F-1): polyether-modified silicone oil (trade name "Toray Silicone SH8400" manufactured by Dow Corning Toray Co., Ltd.)

[0359] Solvent (E-1): Propylene glycol monomethyl ether acetate

[0360] (2) Production of coloring pattern (color filter)

[0361] The colored curable resin composition was applied to a 5 cm square glass substrate (EAGLE 2000; manufactured by CORNING) by spin coating to a film thickness of 3.0 μm after post-baking. The substrate was then pre-baked at 85°C for 2 minutes to form a colored composition layer. After cooling, the substrate with the colored composition layer formed thereon and a quartz glass photomask were separated by a gap of 50 μm. An exposure device (TME-150RSK; manufactured by TOPCON Corporation) was used in an air atmosphere at a temperature of 100 mJ / cm 2 Light irradiation was performed with an exposure dose (365 nm reference). A mask with a 30 μm line and space pattern was used as a photomask. The irradiated colored composition layer was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23°C for 80 seconds, then rinsed with water and post-baked at 85°C for 60 minutes to obtain a colored pattern.

[0362] (3) Film thickness measurement

[0363] The film thickness of the obtained colored pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).

[0364] (4) Chromaticity evaluation

[0365] The resulting colored pattern was measured for spectroscopic spectrum using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation). The xy chromaticity coordinates (x, y) and stimulus value Y in the CIE XYZ colorimetric system were measured using the characteristic function of illuminant C. Furthermore, the xy chromaticity coordinates (x, y) and stimulus value Y were also measured using the same procedure for the colored pattern after irradiation with xenon light in the light resistance evaluation described below.

[0366] (5) Pattern shape evaluation

[0367] The shape of the obtained colored pattern was observed using a scanning electron microscope (S-4000; manufactured by Hitachi High-Technologies Corporation). Figure 1 If the shape shown in (p1) (so-called forward tapered shape) is used, it is marked as ◎, if it is the shape shown in (p2), it is marked as ○, and if it is the shape shown in (p3) (so-called inverted tapered shape), it is marked as ×. If it is the shape shown in (p1) or (p2), there is a trend that the adhesion between the colored pattern and the substrate is further improved. In particular, if it is the shape shown in (p1), the adhesion between the colored pattern and the substrate is further improved, and when a film is laminated on the colored pattern, there is a trend that the film is less likely to crack or peel off. The results are shown in Table 3.

[0368] (6) Light resistance evaluation

[0369] An ultraviolet cut filter (COLORED OPTICAL GLASS L38; manufactured by HOYA; cuts off light of 380 nm or less) was placed on the obtained colored pattern, and the pattern was irradiated with xenon lamp light for 48 hours using a light resistance tester (SUNTEST CPS+; manufactured by Toyo Seiki Co., Ltd.).

[0370] The xy chromaticity coordinates (x, y) and Y were measured before and after irradiation according to the method described in "(4) Chromaticity Evaluation". The color difference ΔE was calculated from the measured values ​​according to the method described in JIS Z 8730:2009 (7. Color difference calculation method). * ab, and the results are shown in Table 3. ΔE * The smaller ab is, the smaller the color change is, that is, △E * The smaller ab is, the better the light resistance is. * If ab is 3 or less, it can be said that there is no problem in practical use as a color filter. * The smaller the ab value, the better.

[0371] (7) Evaluation of solvent resistance

[0372] The resulting colored pattern was immersed in propylene glycol monomethyl ether acetate at room temperature for 10 minutes and then thoroughly rinsed with water. The film thickness was measured before and after immersion using the method described in "(3) Film Thickness Measurement." The change in film thickness before and after immersion was calculated as ΔFT (the film thickness before immersion was set as 100%). The results are shown in Table 3. A smaller absolute value of ΔFT indicates a smaller change in film thickness. If ΔFT is ±3% or less, the colored pattern can be considered to have no practical problems as a color filter.

[0373] [Table 3]

[0374]

[0375] The blue colored pattern obtained in Comparative Example 1 (the same composition as Patent Document 1) had poor shape, insufficient light resistance, and insufficient solvent resistance. In contrast, the blue colored patterns obtained in Examples 1 to 5 had good shapes and exhibited high light resistance and solvent resistance. Furthermore, the green colored pattern obtained in Example 6 had good shapes and improved light resistance and solvent resistance compared to the green colored pattern obtained in Comparative Example 2. Furthermore, the red colored pattern obtained in Example 7 also had good pattern shapes and exhibited high light resistance and solvent resistance.

Claims

1. A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, and a polymerization initiator, The content of the colorant is 10 to 60% by mass in the total solid content of the colored curable resin composition. The polymerization initiator comprises a compound represented by formula (X), In formula (X), R 1 、R 2 and R 3 each independently represents an alkyl group having 1 to 17 carbon atoms, Ar represents a divalent heterocyclic group having 4 or 5 carbon atoms, n represents 0 or 1.

2. The colored curable resin composition according to claim 1, wherein The content of the compound represented by the formula (X) is 0.1 to 50 parts by mass based on 100 parts by mass of the colorant. 3 . A color filter formed from the colored curable resin composition according to claim 1 . A display device comprising the color filter according to claim 3 .

Images