Colored curable resin composition

Abstract

A coloring and curing resin composition, characterized in that it comprises a colorant, a resin, a polymerizable compound, a polymerization initiator, and a solvent, wherein the solvent comprises at least an alkyl diol diacetate having 4 to 6 carbon atoms and an alkyl ester having 2 to 4 carbon atoms of acetic acid, and the content of the alkyl diol diacetate having 4 to 6 carbon atoms is 1% to 20% by mass in 100% by mass of the solvent.

Description

Technical Field

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

[0002] As colored curable resin compositions for forming color filters included in display devices, solid-state imaging devices, and the like, there are known colored curable resin compositions containing a colorant, a binder resin, a polymerizable compound, a polymerization initiator, and a solvent (Patent Documents 1 and 2).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2009-091551

[0006] Patent Document 2: Japanese Patent Application Publication No. 2010-044285 Summary of the invention

[0007] The color filter is composed of a substrate, each color pixel, and a black matrix formed on the substrate and separating the color pixels from each other.

[0008] From the viewpoint of preventing light leakage, the ends of each colored pixel are usually formed in a manner overlapping the black matrix. On the other hand, if the colorant concentration is increased in a color filter requiring high color reproducibility, the colored coating film of each colored pixel existing on the black matrix tends to form protrusions, and it is desired to reduce the amount of colored coating film attached to the black matrix (hereinafter also referred to as the attachment rate).

[0009] An object of the present invention is to provide a colored curable resin composition capable of forming a colored coating film having a reduced adhesion rate of the colored coating film on a black matrix.

[0010] The present invention provides the colored curable resin composition, color filter, display device, and solid-state imaging element shown below.

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

[0012] The solvent contains at least an alkanediol diacetate having 4 to 6 carbon atoms and an alkyl ester of acetic acid having 2 to 4 carbon atoms.

[0013] The content of the alkanediol diacetate having 4 to 6 carbon atoms is 1% by mass to 20% by mass in 100% by mass of the solvent.

[0014] [2] The colored curable resin composition according to [1], wherein the content ratio of the alkanediol diacetate having 4 to 6 carbon atoms / the alkyl ester of acetic acid having 2 to 4 carbon atoms is 0.02 to 1.0.

[0015] [3] The colored curable resin composition according to [1] or [2], wherein the solvent further contains an ether ester solvent having a boiling point of 150° C. or less.

[0016] [4] The colored curable resin composition according to any one of [1] to [3], wherein the content of the above-mentioned colorant is 10% by mass to 55% by mass in 100% by mass of the solid content of the colored curable resin composition, and the above-mentioned colorant includes one or more selected from the group consisting of a red pigment, a green pigment and a blue pigment.

[0017] [5] A color filter formed from the colored curable resin composition according to any one of [1] to [4].

[0018] [6] A color filter characterized in that a pattern is formed on a substrate and a portion of the pattern overlaps with a black matrix, and an adhesion rate represented by a ratio of a thickness (a) of the color filter on the black matrix to a thickness (b) of the color filter on the substrate [(a) / (b)] is less than 0.71.

[0019] [7] A display device comprising the color filter described in [5] or [6].

[0020] [8] A solid-state imaging element comprising the color filter described in [5] or [6].

[0021] According to the present invention, there is provided a colored curable resin composition capable of forming a colored coating film having a reduced adhesion rate of the colored coating film on a black matrix.

[0022] Furthermore, according to the present invention, the yield in manufacturing of a color filter, a display device, a solid-state imaging element, and the like is improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a graph showing the adhesion rate represented by the ratio [(a) / (b)] of the thickness (a) of the color filter on the black matrix to the thickness (b) of the color filter on the substrate. DETAILED DESCRIPTION

[0024] The colored curable resin composition of the present invention contains 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)), a polymerization initiator (hereinafter, sometimes referred to as a polymerization initiator (D)), and a solvent (hereinafter, sometimes referred to as a solvent (E)).

[0025] The colored curable resin composition of the present invention may contain a polymerization initiation aid (hereinafter, sometimes referred to as a polymerization initiation aid (D1)).

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

[0027] 〔1〕Colorant (A)

[0028] The colored curable resin composition of the present invention contains a colorant (A). The colorant (A) preferably contains at least one selected from a dye and a pigment, and more preferably contains a pigment. The colorant (A) may contain one or more kinds.

[0029] 〔pigment〕

[0030] Examples of the pigment include organic pigments and inorganic pigments, and examples include compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists). The pigment may be used alone or in combination of two or more.

[0031] Examples of the pigment include yellow pigments such as CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, and 214;

[0032] CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments;

[0033] CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 202, 209, 215, 216, 224, 242, 254, 255, 264, 265, 269, 291 and other red pigments;

[0034] CI Pigment Blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments;

[0035] CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments;

[0036] CI Pigment Green 7, 36, 58, 59 and other green pigments;

[0037] CI Pigment Brown 23, 25 and other brown pigments;

[0038] Black pigments such as CI Pigment Black 1, 7, etc.

[0039] The pigment may be subjected to rosin treatment, surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, grafting treatment on the pigment surface using a polymer compound, micronization treatment using a sulfuric acid micronization method, or washing treatment using an organic solvent, water, etc. to remove impurities, or removal treatment of ionic impurities using an ion exchange method, etc. The particle size of the pigment is preferably uniform.

[0040] The pigment can be dispersed in a pigment dispersant solution to prepare a pigment dispersion in which the pigment is uniformly dispersed. The pigments can be dispersed individually or in a mixture of multiple types.

[0041] As the pigment dispersant, for example, cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic acid and other pigment dispersants can be cited. These pigment dispersants can be used alone or in combination of two or more. As the pigment dispersant, when expressed by trade name, KP (Shin-Etsu Chemical Co., Ltd.), FLOWLEN (Kyoeisha Chemical Co., Ltd.), Solsperse (Zeneca Co., Ltd.), EFKA (BASF Co., Ltd.), AJISPER (Ajinomoto Fine Chemical Co., Ltd.), Disperbyk (BYK-Chemie Co., Ltd.) and the like can be cited.

[0042] When a pigment dispersant is used, its usage amount is preferably 100 parts by mass or less, more preferably 5 to 50 parts by mass, relative to 100 parts by mass of the pigment. When the usage amount of the pigment dispersant is within the above range, there is a tendency to obtain a uniformly dispersed pigment dispersion.

[0043] The colorant (A) preferably contains one or more selected from a red pigment, a green pigment, and a blue pigment, and preferably further contains a yellow pigment from the viewpoint of adjusting the chromaticity.

[0044] The red pigment more preferably contains at least any one of CI Pigment Red 144, 177, 242, 254, 269 and 291 among the above pigments, more preferably contains at least any one of azo pigments, diketopyrrolopyrrole pigments (same as CI Pigment Red 291), anthraquinone pigments, xanthene pigments and perylene pigments, and particularly preferably contains at least any one of CI Pigment Red 177 and 291. The red pigment may be used in combination with a yellow pigment, an orange pigment or the like.

[0045] The green pigment more preferably contains at least one of the above-mentioned pigments CI Pigment Green 58 and 59. The green pigment may be used together with a yellow pigment.

[0046] The blue pigment more preferably contains at least any one of CI Pigment Blue 15, 15:3, 15:4 and 15:6 among the above pigments, and particularly preferably contains at least CI Pigment Blue 15:6. The blue pigment may be used in combination with a violet pigment or with a dye described below.

[0047] The yellow pigment more preferably contains at least any one of CI Pigment Yellow 129, 138, 139, 150, 185 and 231 among the above pigments, more preferably contains at least any one of quinophthalone pigment, metal-containing pigment and isoindoline pigment, and particularly preferably contains at least CI Pigment Yellow 150.

[0048] 〔dye〕

[0049] As dye, known dye can be used, solvent dye, acid dye, direct dye, mordant dye etc. can be enumerated, for example, compounds classified as solvent, acid, alkaline, active, direct, dispersed, mordant or reduced dyes in the color index (published by The Society of Dyers and Colourists), known dyes recorded in the dyeing guide (color dyeing company) can be enumerated. Dye can be appropriately selected according to the spectral spectrum of the desired color filter. These dyes can be used alone or in combination of more than two. Dye is preferably an organic solvent soluble dye.

[0050] Specific examples of the dye include CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, and 189;

[0051] CI Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;

[0052] CI Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86;

[0053] CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

[0054] CI Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;

[0055] CI solvent dyes such as CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc.

[0056] 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;

[0057] 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;

[0058] CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

[0059] CI Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;

[0060] CI Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123 , 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340;

[0061] CI acid green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109 and other CI acid dyes,

[0062] CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;

[0063] 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;

[0064] CI Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

[0065] CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

[0066] CI Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167 7, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

[0067] CI direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other CI direct dyes,

[0068] CI Disperse Yellow 51, 54, 76;

[0069] CI Disperse Violet 26, 27;

[0070] CI disperse blue 1, 14, 56, 60 and other CI disperse dyes,

[0071] CI Basic Red 1, 10;

[0072] 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;

[0073] CI Basic Violet 2;

[0074] CI Basic Red 9;

[0075] CI basic dyes such as CI basic green 1,

[0076] CI Reactive Yellow 2, 76, 116;

[0077] CI Reactive Orange 16;

[0078] CI reactive dyes such as CI Reactive Red 36,

[0079] CI Medium Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

[0080] 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;

[0081] 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;

[0082] 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;

[0083] 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;

[0084] CI mordant green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53 and other CI mordant dyes,

[0085] CI vat dyes such as CI vat green 1, etc.

[0086] In addition, as dyes, according to their chemical structures, there can be mentioned triarylmethane dyes, xanthene dyes, azo dyes, cyanine dyes, triphenylmethane dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, tetrazoporphyrin dyes, and the like.

[0087] The dye is preferably the following dyes (A1) to (A4).

[0088] 〔Dye (A1)〕

[0089] The dye (A1) includes a salt represented by the formula (A-IV). The dye (A1) also includes a tautomer thereof.

[0090]

[0091] [In formula (A-IV), R 1A ~R 8A Each independently represents a hydrogen atom, a halogen atom, a nitro group, a sulfonyl group, a hydroxyl group, or a saturated hydrocarbon group having 1 to 20 carbon atoms, and an oxygen atom may be inserted between the methylene groups constituting the saturated hydrocarbon group.

[0092] R 9A ~R 12A Each independently represents a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, or a saturated hydrocarbon group having 1 to 20 carbon atoms, and the substituent that the aryl group and the aralkyl group may have may be -SO3 - or -SO2-N - -SO2-R f , an oxygen atom may be inserted between the methylene groups constituting the saturated hydrocarbon group, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted by halogen atoms or amino groups which may have substituents. 9A With R 10A can bond and form a ring with the nitrogen atom to which they are bonded, R 11A With R 12A They may bond to form a ring together with the nitrogen atom to which they are bonded.

[0093] A represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent or an aromatic heterocyclic group having 3 to 20 carbon atoms which may have a substituent, and the substituent which the aromatic hydrocarbon group and the aromatic heterocyclic group may have may be -SO3 - or -SO2-N - -SO2-R f .

[0094] [Y] (m-n)- It represents an arbitrary (m-n)-valent anion.

[0095] m represents any natural number.

[0096] n represents -SO3 as a substituent - or -SO2-N - -SO2-R f The number of is 0 or 1.

[0097] R f represents a fluoroalkyl group having 1 to 12 carbon atoms.]

[0098] R 1A ~R 12A The saturated hydrocarbon group having 1 to 20 carbon atoms represented by may be any of linear, branched and cyclic, and examples thereof include methyl, ethyl, propyl, isopropyl, pentyl, hexyl, 2-ethylhexyl, decyl, dodecyl, eicosyl, cyclohexyl and adamantyl.

[0099] As R 1A ~R 12A The group having a saturated hydrocarbon group having 1 to 20 carbon atoms and an oxygen atom inserted between methylene groups constituting the saturated hydrocarbon group includes the group represented by the following formula: In the following formula, * represents a bonding site to a carbon atom or a nitrogen atom.

[0100] Among them, a saturated hydrocarbon group having 1 to 10 carbon atoms and an oxygen atom inserted between the methylene groups constituting the saturated hydrocarbon group is preferred, and a saturated hydrocarbon group having 1 to 6 carbon atoms and an oxygen atom inserted between the methylene groups constituting the saturated hydrocarbon group is more preferred.

[0101]

[0102] As R 9A ~R 12A The aryl group having 6 to 20 carbon atoms in the group includes phenyl, tolyl, xylyl, naphthyl, anthracenyl, phenanthrenyl, phenylphenyl and the like.

[0103] As R 9A ~R 12A The aralkyl group having 7 to 20 carbon atoms includes benzyl, phenylethyl, methylphenylethyl and the like.

[0104] As R 9A ~R 12A The amino group which may have a substituent includes an amino group having one alkyl group having 1 to 4 carbon atoms, such as methylamino and ethylamino; an amino group having two alkyl groups having 1 to 4 carbon atoms, such as dimethylamino, diethylamino and ethylmethylamino; and an amino group.

[0105] As R 9A ~R 12AThe saturated hydrocarbon group having 1 to 20 carbon atoms which has a halogen atom or an amino group which may have a substituent includes, for example, trifluoromethyl, trifluoroethyl, chloroethyl, bromoethyl, iodoethyl, N,N-dimethylaminoethyl, pentafluoropropyl, chlorohexyl, bromohexyl, iodohexyl and N,N-dimethylaminohexyl.

[0106] R 9A ~R 12A In the aryl group or aralkyl group which may have a substituent, as a substituent, in addition to the above-mentioned -SO3 - or -SO2-N - -SO2-R f In addition, halogen atoms such as fluorine, chlorine and iodine atoms; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; hydroxyl groups; sulfo groups; sulfamoyl groups; alkylsulfonyl groups having 1 to 6 carbon atoms such as methylsulfonyl groups, and the like are also mentioned.

[0107] As R f Examples of the fluoroalkyl group having 1 to 12 carbon atoms include trifluoromethyl and 2,2,2-trifluoroethyl.

[0108] Specific examples of the aryl group which may have a substituent and the aralkyl group which may have a substituent include groups represented by the following formulae: In the following formulae, * represents a bonding site to a nitrogen atom.

[0109]

[0110]

[0111] As R 9A With R 10A The ring formed by bonding together with the nitrogen atom to which they are bonded, and R 11A With R 12A Examples of the ring formed by bonding together with the nitrogen atom to which these are bonded include a pyrrolidine ring, a morpholine ring, a piperidine ring, and a piperazine ring.

[0112] From the perspective of ease of synthesis, R 1A ~R 8A Preferably, each independently is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, and more preferably each independently is a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom.

[0113] From the perspective of ease of synthesis, R 9A ~R 12APreferably, each independently represents a saturated hydrocarbon group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may be substituted. More preferably, each independently represents a saturated hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 15 carbon atoms which may have a substituent, or an aryl group having 6 to 12 carbon atoms which may be substituted, and the hydrogen atoms contained in the aralkyl group and the aryl group may be substituted with a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a sulfo group, or an alkylsulfonyl group having 1 to 4 carbon atoms. Further preferably, each independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a benzyl group, and the hydrogen atoms contained in the phenyl group and the benzyl group may be substituted with a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a sulfo group, or an alkylsulfonyl group having 1 to 4 carbon atoms. Examples of the phenyl group and the benzyl group include groups represented by the following formulae. In the following formula, * represents a bonding site to a nitrogen atom.

[0114]

[0115]

[0116] Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms in A include phenyl, tolyl, xylyl, naphthyl, anthracenyl, phenanthrenyl, and phenylphenyl.

[0117] Examples of the aromatic hydrocarbon group which may have a substituent and which is represented by A include groups represented by the following formulae: * represents a bonding site to a carbon atom.

[0118]

[0119] The aromatic heterocyclic group represented by A refers to an aromatic group having at least one heteroatom as a ring constituent. Examples of the heteroatom include a nitrogen atom, an oxygen atom, and a sulfur atom.

[0120] A is preferably an aromatic heterocyclic group having at least one nitrogen atom as a ring constituent. Examples of the aromatic heterocyclic group include five-membered aromatic heterocyclic groups having a nitrogen atom such as pyrrolyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, and triazolyl; six-membered aromatic heterocyclic groups having a nitrogen atom such as pyridyl, pyridinyl, and pyridazinyl; and condensed-ring aromatic heterocyclic groups such as benzimidazolyl and indolyl.

[0121] Examples of the substituent in A include a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a sulfo group, a sulfamoyl group, an alkylsulfonyl group having 1 to 6 carbon atoms, and an amino group which may have a substituent. Specifically, examples include 9A ~R 12A The same substituents as exemplified in .

[0122] A is preferably a group represented by formula (t1).

[0123]

[0124] [In formula (t1),

[0125] R 56 It represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

[0126] X2 represents -O-, -N(R 57 )-or-S-.

[0127] R 57 It represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0128] R 45 and R 46 Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent. When the saturated hydrocarbon group has 2 to 20 carbon atoms, the -CH2- contained in the saturated hydrocarbon group may be substituted with at least one of -O- and -CO-. In the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent -CH2- are not substituted with -O- at the same time, and the terminal -CH2- is not substituted with -O- or -CO-. R 45 With R 46 They may bond to form a ring together with the nitrogen atom to which they are bonded.

[0129] *Indicates the bonding site to the carbocation.]

[0130] As the aromatic heterocyclic group which may have a substituent and represents A, groups represented by the following formulae are mentioned: * represents a bonding site to a carbon atom.

[0131]

[0132] X2 is preferably -S-.

[0133] R 56 An aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent is preferred, and a phenyl group which may have a substituent is more preferred.

[0134] R 45 and R 46Preferably, each is independently a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, more preferably each is independently an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, and further preferably one is an alkyl group having 1 to 6 carbon atoms which may have a substituent and the other is an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent.

[0135] A is preferably a group represented by formula (A1-12) and formula (A1-13).

[0136] As [Y] (m-n) -, known anions can be mentioned, and from the viewpoint of heat resistance, boron-containing anions, aluminum-containing anions, fluorine-containing anions, and anions containing at least one element selected from tungsten, molybdenum, silicon and phosphorus and oxygen are preferred.

[0137] Examples of the boron-containing anion and the aluminum-containing anion include anions represented by the following formula (4).

[0138]

[0139] [In formula (4), W 1 and W 2 Each independently represents a group having at least two monovalent proton donor substituents and two substituents which release protons from the group. M represents a boron atom or an aluminum atom.]

[0140] As a group having at least two monovalent proton donor substituents and having two substituents formed by releasing protons from the group, a group formed by releasing protons from two proton donor substituents in a compound having at least two monovalent proton donor substituents (e.g., hydroxyl, carboxyl, etc.) can be cited. As such a compound, preferably catechol 2,3-dihydroxynaphthalene, 2,2'-biphenol, 3-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-hydroxy-2-naphthoic acid, binaphthol, salicylic acid, benzilic acid or mandelic acid can be cited, and they may have a substituent.

[0141] Examples of the substituent include a halogen atom; an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a nitro group; a hydroxyl group; and an amino group.

[0142] Examples of the anion represented by the formula (4) include anions represented by the following formulae.

[0143]

[0144] [Where R 61 , R 62 , R 63 and R64 Each independently represents a hydrogen atom, a hydroxyl group, an amino group, a nitro group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.]

[0145] For example, the following anions (BC-1) to (BC-28) are mentioned. M represents a boron atom or an aluminum atom. tBu in Table 1 represents a tert-butyl group.

[0146] [Table 1]

[0147] Anions <![CDATA[R 61 ]]> <![CDATA[R 62 ]]> <![CDATA[R 63 ]]> <![CDATA[R 64 ]]> Anion (BC-1) H H H H Anion (BC-2) OH H H H Anion (BC-3) H OH H H Anion (Bc-4) H H OH H Anion (BC-5) H H H OH Anion (BC-6) Cl H H H Anion (BC-7) H Cl H H Anion (BC-8) H H Cl H Anion (BC-9) H H H Cl Anion (BC-10) Br H H H Anion (BC-11) H Br H H Anion (BC-12) H H Br H Anion (BC-13) H H H Br Anion (BC-14) <![CDATA[NH2]]> H H H Anion (BC-15) H <![CDATA[NH2]]> H H Anion (BC-16) H H <![CDATA[NH2]]> H Anion (BC-17) H H H <![CDATA[NH2]]> Anion (BC-18) H tBu H tBu Anion (BC-19) H Cl H Cl Anion (BC-20) H Br H Br Anion (BC-21) H I H I Anion (BC-22) H OH OH H Anion (BC-23) OH H OH H Anion (BC-24) Cl Cl H Cl

[0148]

[0149] Examples of the fluorine-containing anion include anions represented by the following formula (6), (7), (8) or (9).

[0150]

[0151] [In formula (6), W 3 and W 4 Each independently represents a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or, W 3 With W 4 bonded to form a fluorinated alkanediyl group having 1 to 4 carbon atoms.]

[0152]

[0153] [In formula (7), W 5 , W 6 and W 7 Each independently represents a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms.]

[0154]

[0155] [In formula (8), Y 1 It represents a fluorinated alkanediyl group having 1 to 4 carbon atoms.

[0156]

[0157] [In formula (9), Y 2 represents a fluorinated alkyl group having 1 to 4 carbon atoms.]

[0158] As W in equations (6) and (7) 3 ~W 7The fluoroalkyl groups each representing a carbon number of 1 to 4 are preferably perfluoroalkyl groups, and examples thereof include -CF3, -CF2CF3, -CF2CF2CF3, -CF(CF3)2, -CF2CF2CF2CF3, -CF2CF(CF3)2, and -C(CF3)3.

[0159] As W in formula (6) 3 With W 4 The fluorinated alkanediyl group having 2 to 4 carbon atoms formed by the bonding is preferably a perfluoroalkanediyl group, and examples thereof include -CF2CF2-, -CF2CF2CF2-, and -CF2CF2CF2CF2-.

[0160] As Y in formula (8) 1 The fluorinated alkanediyl group having 1 to 4 carbon atoms represented by is preferably a perfluoroalkanediyl group, and examples thereof include -CF2-, -CF2CF2-, -CF2CF2CF2-, -C(CF3)2-, and -CF2CF2CF2CF2-.

[0161] As Y in formula (9) 2 The fluorinated alkyl group having 1 to 4 carbon atoms represented by is preferably a perfluoroalkyl group, and examples thereof include -CF3, -CF2CF3, -CF2CF2CF3, -CF(CF3)2, -CF2CF2CF2CF3, -CF2CF(CF3)2, and -C(CF3)3.

[0162] Examples of the anion represented by the formula (6) (hereinafter sometimes referred to as “anion (6)”) include the following anions (6-1) to (6-6).

[0163]

[0164] Examples of the anion represented by the formula (7) (hereinafter sometimes referred to as “anion (7)”) include the following anion (7-1).

[0165]

[0166] Examples of the anion represented by the formula (8) (hereinafter sometimes referred to as “anion (8)”) include the following anions (8-1) to (8-4).

[0167]

[0168] Examples of the anion represented by the formula (9) (hereinafter sometimes referred to as “anion (9)”) include the following anions (9-1) to (9-4).

[0169]

[0170] [Y](m-n)- Preferably, it contains at least one element selected from tungsten, molybdenum, silicon and phosphorus, and an anion of oxygen. (m-n)- , preferably the anion of a heteropoly acid or an isopoly acid, more preferably the anion of phosphotungstic acid, silicotungstic acid and tungsten-based isopoly acid.

[0171] Examples of anions of such heteropolyacids or isopolyacids containing tungsten include Keggin-type phosphotungstate ions α-[PW 12 O 40 ] 3- 、Dawson type phosphotungstate ion α-[P2W 18 O 62 ] 6- ,β-[P2W 18 O 62 ] 6- 、Keggin type silicotungstate ion α-[SiW 12 O 40 ] 4- ,β-[SiW 12 O 40 ] 4- ,γ-[SiW 12 O 40 ] 4- , and as another example [P2W 17 O 61 ] 10- 、[P2W 15 O 56 ] 12- 、[H2P2W 12 O 48 ] 12- 、[NaP5W 30 O 110 ] 14- ,α-[SiW9O 34 ] 10- ,γ-[SiW 10 O 36 ] 8- ,α-[SiW 11 O 39 ] 8- ,β-[SiW 11 O 39 ] 8- 、[W6O 19 ] 2- , [W 10 O 32 ] 4- WO4 2- wait.

[0172] Examples of anions composed of at least one element selected from silicon and phosphorus and oxygen include SiO3 2- PO4 3- .

[0173] In particular, from the perspective of ease of synthesis and post-treatment, heteropoly acid anions such as Keggin type phosphotungstate ions, Dawson type phosphotungstate ions, and Keggin type silicotungstate ions are preferred. 10 O 32 ] 4- Equivalent to polyacid anions.

[0174] Specific examples of the salt represented by formula (A-IV) include salts represented by the following formulae (A-IV-1) to (A-IV-26).

[0175]

[0176]

[0177]

[0178]

[0179] The dye (A1) preferably contains a salt represented by the formula (A-IV-26).

[0180] When a sulfonic acid group (-SO3H) is used as a substituent, a hydrogen ion may be exchanged with an arbitrary cation to form a salt. As the arbitrary cation, an alkali metal ion, an organic ammonium ion, an imidazolium ion which may have a substituent, etc. may be mentioned. When a plurality of sulfonic acid groups are used, a salt may be formed with a divalent or higher metal ion.

[0181] 〔Dye (A2)〕

[0182] The dye (A2) includes a xanthene dye. As the xanthene dye, a known one can be used. Hereinafter, the dye (A2) is also referred to as a xanthene dye (A2).

[0183] Xanthene dye (A2) is a dye containing a compound having a xanthene skeleton in the molecule. As xanthene dye (A2), for example, CI Acid Red 51 (hereinafter, CI Acid Red is omitted, and only the number is recorded. The same applies to others), 52, 87, 92, 94, 289, 388, CI Acid Violet 9, 30, 102, CI Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, CI Basic Red 10, 11, CI Basic Violet 10 (Rhodamine B), 11, CI Solvent Red 218, CI Mordant Red 27, CI Reactive Red 36 (Bengal Rose Red B), sulforhodamine G, xanthene dyes recorded in Japanese Patent Publication No. 2010-32999, and xanthene dyes recorded in Patent Publication No. 4492760, etc. are mentioned. Preferably, the xanthene dye is dissolved in an organic solvent.

[0184] Among them, as the xanthene dye (A2), a dye containing a compound represented by formula (1a) (hereinafter, sometimes referred to as "compound (1a)") is preferred. Compound (1a) may also be a tautomer thereof. When compound (1a) is used, the content of compound (1a) in the xanthene dye (A2) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, as the xanthene dye (A2), it is preferred to use only compound (1a).

[0185]

[0186] [In formula (1a), R 1a ~R 4a Each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, wherein the -CH2- in the saturated hydrocarbon group may be replaced by -O-, -CO- or -NR 11a -Replace. 1a and R 2a can form a ring containing nitrogen atoms, R 3a and R 4a They may come together to form a ring containing a nitrogen atom.

[0187] R 5a Indicates -OH, -SO3 - , -SO3H, -SO3 - Za + , -CO2H, -CO2 - Za + , -CO2R 8a ,-SO3R 8a or -SO2NR 9a R 10a .

[0188] R 6a and R 7a Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0189] m represents an integer of 0 to 5. When m is 2 or more, a plurality of R 5a Can be the same or different.

[0190] a represents an integer of 0 or 1.

[0191] Xa represents a halogen atom.

[0192] Za + express + N(R 11a 4. Na + or K + , 4 Rs 11a Can be the same or different.

[0193] R 8a It represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and hydrogen atoms contained in the saturated hydrocarbon group may be substituted with halogen atoms.

[0194] R 9a and R 10a Each independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, wherein the -CH2- in the saturated hydrocarbon group may be -O-, -CO-, -NH- or -NR 8a - Replacement, R 9a and R 10a They may be bonded to each other to form a heterocyclic ring having three to ten members including a nitrogen atom.

[0195] R 11a represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.]

[0196] In formula (1a), there is -SO3 - , its number is 1.

[0197] As R 1a ~R 4a Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include phenyl, tolyl, xylyl, mesityl, propylphenyl and butylphenyl.

[0198] Examples of the substituent that the aromatic hydrocarbon group may have include a halogen atom, a carboxyl group, a -R 8a , -OH, -OR 8a , -SO3 - , -SO3H, -SO3 - Za +, -CO2H, -CO2R 8a , -SR 8a , -SO2R 8a ,-SO3R 8a or -SO2NR 9a R 10a .

[0199] Among them, as a substituent, -SO3 is preferred - , -SO3H, -SO3 - Za + and -SO2NR 9a R 10a , more preferably -SO3 - Za + and -SO2NR 9a R 10a As the -SO3 - Za + , preferably -SO3 -+ N(R 11a )4.

[0200] As R 1a ~R 4a and R 8a ~R 11a The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in the group includes, for example, a straight-chain alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, eicosyl, etc.; a branched-chain alkyl group such as isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl, etc.; and an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, etc.

[0201] R 1a ~R 4a The hydrogen atom contained in the saturated hydrocarbon group in may be substituted with, for example, a carboxyl group, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom.

[0202] R 9a and R 10a The hydrogen atoms contained in the saturated hydrocarbon group may be substituted by, for example, a hydroxyl group or a halogen atom.

[0203] As R 1a and R 2a The ring formed together, and R 3a and R 4a Examples of the ring formed together include the following rings.

[0204]

[0205] AS - OR 8aFor example, there can be mentioned a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group and an eicosyloxy group.

[0206] As -CO2R 8a For example, there can be mentioned a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group and an eicosyloxycarbonyl group.

[0207] As SR 8a For example, there can be mentioned a methylthio group, an ethylthio group, a butylthio group, a hexylthio group, a decylthio group and an eicosylthio group.

[0208] AS-SO2R 8a For example, there can be mentioned a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group and an eicosylsulfonyl group.

[0209] AS-SO3R 8a For example, there can be mentioned a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group and an eicosylsulfonyl group.

[0210] As - SO2NR 9a R 10a , for example, sulfamoyl;

[0211] N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl, N-butylsulfamoyl, N-isobutylsulfamoyl, N-sec-butylsulfamoyl, N-tert-butylsulfamoyl, N-pentylsulfamoyl, N-(1-ethylpropyl)sulfamoyl, N-(1,1-dimethylpropyl)sulfamoyl, N-(1,2-dimethylpropyl)sulfamoyl, N-(2,2-dimethylpropyl)sulfamoyl, N-(1-methylbutyl)sulfamoyl, N-(2-methylbutyl)sulfamoyl, N N-1 substituted sulfamoyl groups such as N-(3-methylbutyl)sulfamoyl, N-cyclopentylsulfamoyl, N-hexylsulfamoyl, N-(1,3-dimethylbutyl)sulfamoyl, N-(3,3-dimethylbutyl)sulfamoyl, N-heptylsulfamoyl, N-(1-methylhexyl)sulfamoyl, N-(1,4-dimethylpentyl)sulfamoyl, N-octylsulfamoyl, N-(2-ethylhexyl)sulfamoyl, N-(1,5-dimethyl)hexylsulfamoyl and N-(1,1,2,2-tetramethylbutyl)sulfamoyl;

[0212] N,N-2-substituted sulfamoyl groups such as N,N-dimethylsulfamoyl, N,N-ethylmethylsulfamoyl, N,N-diethylsulfamoyl, N,N-propylmethylsulfamoyl, N,N-isopropylmethylsulfamoyl, N,N-tert-butylmethylsulfamoyl, N,N-butylethylsulfamoyl, N,N-bis(1-methylpropyl)sulfamoyl and N,N-heptylmethylsulfamoyl.

[0213] R 5a Preferred -CO2H, -CO2 - Za + , -CO2R 8a , -SO3 - , -SO3 - Za + , -SO3H or -SO2NHR 9a , more preferably -SO3 - , -SO3 - Za + , -SO3H or -SO2NHR 9a .

[0214] m is preferably 1 to 4, more preferably 1 or 2.

[0215] As R 6a and R 7a The alkyl group having 1 to 6 carbon atoms in the alkyl group may include the alkyl group having 1 to 6 carbon atoms among the alkyl groups exemplified above.

[0216] As R 11a The aralkyl group having 7 to 10 carbon atoms includes benzyl, phenylethyl, phenylbutyl and the like.

[0217] Za + for + N(R 11a 4. Na + or K + , preferably + N(R 11a )4.

[0218] As the above + N(R 11a ) 4, preferably 4 R 11a At least two of them are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. 11a The total number of carbon atoms is preferably 20-80, more preferably 20-60.

[0219] As compound (1a), a compound represented by formula (2a) (hereinafter sometimes referred to as "compound (2a)") is preferred. Compound (2a) may be a tautomer thereof.

[0220]

[0221] [In formula (2a), R 21a ~R 24a Each independently represents a hydrogen atom, -R 26a or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. 21a and R 22a can form a ring containing nitrogen atoms, R 23a and R 24a They may come together to form a ring containing a nitrogen atom.

[0222] R 25a Indicates - SO3 - , -SO3H, -SO3 - Z1 + or -SO2NHR 26a .

[0223] m1 represents an integer of 0 to 5. When m1 is 2 or more, a plurality of R 25a Can be the same or different.

[0224] a1 represents an integer of 0 or 1.

[0225] X1 represents a halogen atom.

[0226] R 26a It represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a halogen atom or a carboxyl group.

[0227] Z1 + express + N(R 27a 4. Na + or K + , 4 Rs 27a Can be the same or different.

[0228] R 27a It represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group.]

[0229] As R 21a ~R 24a The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in the above R 1a ~R 4a The same groups as those mentioned for the aromatic hydrocarbon groups. The hydrogen atoms contained in the aromatic hydrocarbon groups can be replaced by -SO3 - , -SO3H, -SO3 - Z1 + ,-SO3R 26a or -SO2NHR 26a replace.

[0230] As R 21a ~R 24a Combination of R 21a and R 23a are independently a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms (the saturated hydrocarbon group may have a halogen atom or a carboxyl group), R 22a and R 24a A monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, wherein the hydrogen atoms contained in the aromatic hydrocarbon group are replaced by -SO3 - , -SO3H, -SO3 - Z1 + ,-SO3R 26a or -SO2NHR 26a A further preferred combination is R 21a and R 23a are independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (the alkyl group may have a halogen atom or a carboxyl group), R 22a and R 24a A monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, wherein the hydrogen atoms contained in the aromatic hydrocarbon group are replaced by -SO3 - Z1 + or -SO2NHR 26a Replacement combination.

[0231] As R 21a and R 22a Together, they form a ring containing a nitrogen atom, and R 23a and R 24a The ring containing nitrogen atoms formed together with R 1a and R 2a The ring formed together is the same ring. Among them, an aliphatic heterocycle is preferred. As the aliphatic heterocycle, for example, the following examples can be mentioned.

[0232]

[0233] As R 26a and R 27a The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in the 8a ~R 11a The same groups as those exemplified as the saturated hydrocarbon group in .

[0234] R 21a ~R 24a For -R 26a When -R 26a Preferably, each independently is a methyl group or an ethyl group. 26a and -SO2NHR 26a R 26a, preferably a branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 6 to 12 carbon atoms, and further preferably a 2-ethylhexyl group.

[0235] Z1 + for + N(R 27a 4. Na + or K + , preferably + N(R 27a )4.

[0236] As the above + N(R 27a ) 4, preferably 4 R 27a At least two of them are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. 27a The total number of carbon atoms is preferably 20-80, more preferably 20-60.

[0237] m1 is preferably 1 to 4, more preferably 1 or 2.

[0238] In addition, as compound (1a), a compound represented by formula (3a) (hereinafter sometimes referred to as "compound (3a)") is also preferred. Compound (3a) may be a tautomer thereof.

[0239]

[0240] [In formula (3a), R 31a and R 32a Each independently represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, wherein the hydrogen atom contained in the saturated hydrocarbon group may be substituted by an aromatic hydrocarbon group having 6 to 10 carbon atoms, a carboxyl group or a halogen atom, wherein the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by an alkoxy group having 1 to 3 carbon atoms, and the -CH2- contained in the above saturated hydrocarbon group may be substituted by -O-, -CO- or -NR 11a -replace.

[0241] R 33a and R 34a Each independently represents an alkyl group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.

[0242] R 31a and R 33a can form a ring containing nitrogen atoms, R 32a and R 34a They may come together to form a ring containing a nitrogen atom.

[0243] p and q each independently represent an integer of 0 to 5. When p is 2 or more, a plurality of R 33aThey may be the same or different. When q is 2 or more, multiple R 34a Can be the same or different.

[0244] R 11a Means the same as above.]

[0245] As R 31a and R 32a The monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in the 8a A group having 1 to 10 carbon atoms in a monovalent saturated hydrocarbon group.

[0246] Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be present as a substituent include: 1a The same group as the aromatic hydrocarbon group in.

[0247] Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group.

[0248] R 31a and R 32a Preferably, they are independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms (the saturated hydrocarbon group may have a halogen atom or a carboxyl group).

[0249] As R 33a and R 34a The alkyl group having 1 to 4 carbon atoms in the alkyl group includes methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-propyl, tert-butyl and the like.

[0250] As R 33a and R 34a The alkylthio group having 1 to 4 carbon atoms includes methylthio, ethylthio, propylthio, butylthio and isopropylthio.

[0251] As R 33a and R 34a Examples of the alkylsulfonyl group having 1 to 4 carbon atoms include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl and isopropylsulfonyl.

[0252] R 33a and R 34a An alkyl group having 1 to 4 carbon atoms is preferred, and a methyl group is more preferred.

[0253] p and q are preferably integers of 0 to 2, and preferably 0 or 1.

[0254] Examples of the compound (1a) include compounds represented by formula (1-1) to formula (1-107). 40aR represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group. 26a has the same R as in formula (2a) 26a Same meaning.

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267] Among the above compounds, the compounds represented by formula (1-1) to formula (1-23), formula (1-37) to formula (1-85) and formula (1-102) to formula (1-107) are equivalent to compound (2a), and the compounds represented by formula (1-24) to formula (1-36) and formula (1-86) to formula (1-101) are equivalent to compound (3a).

[0268] Among them, preferred are sulfonamides of CI Acid Red 289, quaternary ammonium salts of CI Acid Red 289, sulfonamides of CI Acid Violet 102, and quaternary ammonium salts of CI Acid Violet 102. Examples of such compounds include compounds represented by formula (1-1) to (1-8), formula (1-11), and formula (1-12).

[0269] In addition, compounds represented by formula (1-24) to formula (1-33) are also preferred because of their excellent solubility in organic solvents.

[0270] From the viewpoint that the chromaticity range and transmittance of the obtained coating film are good, compounds represented by formula (1-32), formula (1-44) and formula (1-97) are also preferred.

[0271] The xanthene dye (A2) can be a commercially available xanthene dye (e.g., "Chugai Aminol Fast Pink R-H / C" manufactured by Chugai Chemical Co., Ltd., "Rhodamin 6G" manufactured by Taoka Chemical Industry Co., Ltd.) Alternatively, a commercially available xanthene dye can be used as a starting material and synthesized with reference to Japanese Patent Application Laid-Open No. 2010-32999.

[0272] 〔Dye (A3)〕

[0273] The dye (A3) includes an anthraquinone dye. A known anthraquinone dye can be used. Examples of the anthraquinone dye include:

[0274] CI Solvent Yellow 117 (hereinafter, CI Solvent Yellow, etc. are omitted, and only the number is recorded), 163, 167, 189,

[0275] CI Solvent Orange 77, 86,

[0276] CI Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247,

[0277] CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60,

[0278] CI Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139,

[0279] CI Solvent Green 3, 28, 29, 32, 33,

[0280] CI Acid Red 80,

[0281] CI Acid Green 25, 27, 28, 41,

[0282] CI Acid Violet 34,

[0283] CI Acid Blue 25, 27, 40, 45, 78, 80, 112,

[0284] CI Disperse Yellow 51,

[0285] CI Disperse Violet 26, 27,

[0286] CI Disperse Blue 1, 14, 56, 60,

[0287] CI Direct Blue 40,

[0288] CI Medium Red 3, 11,

[0289] CI Media Blue 8, etc.

[0290] The anthraquinone dye is preferably dissolved in an organic solvent.

[0291] 〔Dye(A4)〕

[0292] The dye (A4) includes a porphyrazine dye. A porphyrazine dye is a compound having a porphyrazine skeleton in the molecule. When the porphyrazine dye is an acid dye or a basic dye, it may form a salt with any cation or anion.

[0293] The content of the colorant (A) in the colored curable resin composition is preferably 5% to 70% by mass, more preferably 5% to 60% by mass, and further preferably 5% to 50% by mass relative to the total amount of the solid content in the colored curable resin composition. When the content of the colorant (A) is within the above range, a desired spectrum and color density can be obtained.

[0294] In this specification, the "total amount of solids in the colored curable resin composition" refers to the total amount of the components obtained by removing the solvent (E) from the colored curable resin composition. The total amount of solids and the content of each component relative to the total amount of solids can be measured by known analytical means such as liquid chromatography or gas chromatography.

[0295] The colorant (A) preferably contains the above-mentioned pigment and at least one selected from the group consisting of dyes (A1) to (A4).

[0296] When the colorant (A) contains the dye (A1), the colorant (A) may be contained in the form of a dispersion in which the dye (A1) is dispersed in a solvent.

[0297] In addition, in another embodiment, the colorant (A) preferably comprises a pigment and a xanthene dye (A2), more preferably comprises a pigment and a compound represented by the above formula (1a), further preferably comprises a pigment and a compound represented by the above formula (2a), particularly preferably comprises a pigment and a compound represented by the above formula (3a), and even more particularly preferably comprises a pigment and at least one selected from the group consisting of a compound represented by the above formula (1-32), a compound represented by the formula (1-44), and a compound represented by the formula (1-97).

[0298] When the colorant (A) contains the dye (A1), the content of the dye (A1) in the colorant (A) is preferably 0.5 to 100% by mass, more preferably 61 to 99.5% by mass, and even more preferably 81 to 99% by mass.

[0299] When the colorant (A) contains the dye (A2), the content of the dye (A2) in the colorant (A) is preferably 0.1 to 80% by mass, more preferably 0.3 to 40% by mass, and even more preferably 0.5 to 20% by mass.

[0300] When the colorant (A) contains the dyes (A1) and (A2), the mass ratio of the dye (A1) to the dye (A2) in the colorant (A) [(A1):(A2)] may be, for example, 0.01:99.99 to 99.99:0.01, preferably 50:50 to 99.95:0.05, and more preferably 90:10 to 99.9:0.1.

[0301] When the colorant (A) contains a dye (A2) and a pigment, the mass ratio of the dye (A2) to the pigment in the colorant (A) [(A2): pigment] may be, for example, 1:99 to 99:1, preferably 5:95 to 50:50, and more preferably 10:90 to 30:70.

[0302] When the colored curable resin composition contains a solvent (hereinafter, also referred to as solvent (E)), a liquid containing a colorant including a colorant (A) and a solvent (E) may be prepared in advance, and then the liquid containing the colorant may be used to prepare the colored curable resin composition. When the colorant (A) is not dissolved in the solvent (E), the liquid containing the colorant may be prepared as a dispersion by dispersing and mixing the colorant (A) in the solvent (E). The liquid containing the colorant may contain a part or all of the solvent (E) contained in the colored curable resin composition.

[0303] The content of the solid component in the liquid containing the colorant is preferably 0.1% to 99.9% by mass, more preferably 1% to 90% by mass, further preferably 1% to 60% by mass, and particularly preferably 3% to 50% by mass, relative to the total amount of the liquid containing the colorant.

[0304] The content of the colorant (A) in the colorant-containing liquid is preferably 0.01% by mass to 100% by mass, more preferably 0.1% by mass to 99.9% by mass, further preferably 1% by mass to 99% by mass, and particularly preferably 10% by mass to 90% by mass, based on the total amount of solid components in the colorant-containing liquid.

[0305] In this specification, the "total amount of solid components in the liquid containing the colorant" refers to the total amount of components obtained by removing the solvent (E) from the liquid containing the colorant. The total amount of solid components and the content of each component relative to the total amount of solid components can be measured using known analytical methods such as liquid chromatography or gas chromatography.

[0306] The colorant (A) may be dispersed by containing a dispersant so that the colorant (A) is uniformly dispersed in the liquid containing the colorant.

[0307] As dispersant, surfactant etc. can be enumerated, and can be any surfactant in cationic, anionic, nonionic and amphoteric. Specifically, surfactants such as polyester, polyamine and acrylic acid can be enumerated. These dispersants can be used alone or in combination of two or more. As dispersant, when represented 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 (Strain) system), AJISPER (registered trademark) (Ajinomoto Fine Chemicals (Strain) system) and Disperbyk (registered trademark) (BYK-Chemie (Strain) system), BYK (registered trademark) (BYK-Chemie (Strain) system) etc. can be enumerated.

[0308] In order to prepare the above-mentioned colorant-containing liquid, when a dispersant is used, the amount of the dispersant (solid content) used is preferably 5 to 100 parts by mass, more preferably 5 to 50 parts by mass, relative to 100 parts by mass of the colorant (A). When the amount of the dispersant used is within the above range, there is a tendency to obtain a colorant-containing liquid in a more uniform dispersed state.

[0309] 〔2〕Resin (B)

[0310] The colored curable resin composition contains a resin [hereinafter also referred to as resin (B)].

[0311] The resin (B) is preferably an alkali-soluble resin. Alkali solubility refers to the property of being soluble in an aqueous solution of an alkaline compound, that is, a developer. Examples of the resin (B) include the following resins [K1] to [K6].

[0312] Resin [K1]: A copolymer having a structural unit derived from at least one selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as "monomer (a)"), and a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b)").

[0313] Resin [K2]: A copolymer having a structural unit derived from monomer (a), a structural unit derived from monomer (b), and a structural unit derived from a monomer copolymerizable with monomer (a) (which is different from monomer (a) and monomer (b)) [hereinafter sometimes referred to as "monomer (c)"].

[0314] Resin [K3]: A copolymer having a structural unit derived from the monomer (a) and a structural unit derived from the monomer (c).

[0315] Resin [K4]: A resin having a structural unit obtained by adding a monomer (b) to a copolymer having structural units derived from the monomer (a) and the monomer (c).

[0316] Resin [K5]: A resin having a structural unit obtained by adding a monomer (a) to a copolymer having structural units derived from a monomer (b) and a monomer (c).

[0317] Resin [K6]: A resin having a structural unit obtained by adding a monomer (a) to a copolymer having structural units derived from monomers (b) and (c), and further having a structural unit to which carboxylic anhydride is added.

[0318] The above-mentioned resins [K1] to [K6] may be the following copolymers or resins.

[0319] Resin [K1]: A copolymer of monomer (a) and monomer (b).

[0320] Resin [K2]: A copolymer of monomer (a), monomer (b) and monomer (c).

[0321] Resin [K3]: A copolymer of monomer (a) and monomer (c).

[0322] Resin [K4]: A resin obtained by reacting a copolymer of monomer (a) and monomer (c) with monomer (b).

[0323] Resin [K5]: A resin obtained by reacting a copolymer of monomer (b) and monomer (c) with monomer (a).

[0324] Resin [K6]: A resin obtained by reacting a copolymer of a monomer (b) and a monomer (c) with a monomer (a), and further reacting with a carboxylic anhydride.

[0325] Specific examples of the monomer (a) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexanephthalic acid, unsaturated dicarboxylic acids such as enedicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (nadic anhydride); unsaturated mono[(meth)acryloyloxyalkyl] esters of polycarboxylic acids having a valence of 2 or more such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate; unsaturated (meth)acrylic acid containing a hydroxyl group and a carboxyl group in the same molecule such as α-(hydroxymethyl)acrylic acid, etc.

[0326] Among them, (a) is preferably (meth)acrylic acid, maleic anhydride, or the like, from the viewpoint of copolymerization reactivity and solubility in aqueous alkali solution.

[0327] In addition, in this specification, "(meth)acrylic acid" means at least one selected from acrylic acid and methacrylic acid. The same applies to "(meth)acryloyl" and "(meth)acrylate".

[0328] Monomer (b) refers to a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring)) and an ethylenically unsaturated bond. Monomer (b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0329] Examples of the monomer (b) include a monomer having an oxetane group and an ethylenically unsaturated bond [hereinafter, sometimes referred to as "monomer (b1)"], a monomer having an oxetane group and an ethylenically unsaturated bond [hereinafter, sometimes referred to as monomer "(b2)"], a monomer having a tetrahydrofuran group and an ethylenically unsaturated bond [hereinafter, sometimes referred to as "monomer (b3)"], and the like.

[0330] Examples of (b1) include monomers having a structure in which an unsaturated aliphatic hydrocarbon is epoxidized (hereinafter, sometimes referred to as "monomer (b1-1)") and monomers having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized (hereinafter, sometimes referred to as "monomer (b1-2)").

[0331] Examples of the monomer (b1-1) include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α-methyl-p-vinyl benzyl glycidyl ether, 2,3-bis(glycidyl)acrylate, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tri(glycidyloxymethyl)styrene, 2,3,5-tri(glycidyloxymethyl)styrene, 2,3,6-tri(glycidyloxymethyl)styrene, 3,4,5-tri(glycidyloxymethyl)styrene, 2,4,6-tri(glycidyloxymethyl)styrene, etc.

[0332] Examples of the monomer (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), a compound represented by formula (I), a compound represented by formula (II), and the like.

[0333]

[0334] In formula (I) and formula (II), R aa and R ab Each of X independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, wherein the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group. a1 and Xa2 Independently of each other, they represent single bonds, *-R ac -, * - R ac -O-, *-R ac -S-, or *-R ac -NH-. ac It represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bonding site with O.

[0335] 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 and tert-butyl group.

[0336] 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.

[0337] R aa and R ab Preferred are a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferred are a hydrogen atom and a methyl group.

[0338] As a component of R ac The alkanediyl group includes a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group and the like.

[0339] X a1 and X a2 Preferred are a single bond, a methylene group, an ethylene group, a *-CH2-O- (* represents a bonding site to O) group, and a *-CH2CH2-O- group, and more preferred are a single bond and a *-CH2CH2-O- group.

[0340] Specific examples of the compound represented by formula (I) include compounds represented by formula (I-1) to formula (I-15), preferably compounds represented by formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), and formula (I-11) to formula (I-15), and more preferably compounds represented by formula (I-1), formula (I-7), formula (I-9), and formula (I-15).

[0341]

[0342] Specific examples of the compound represented by formula (II) include compounds represented by formula (II-1) to formula (II-15), preferably compounds represented by formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), formula (II-11) to formula (II-15), and more preferably compounds represented by formula (II-1), formula (II-7), formula (II-9) and formula (II-15).

[0343]

[0344] The compound represented by formula (I) and the compound represented by formula (II) can be used separately. They can be mixed in any ratio. When mixed, the mixing ratio is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and further preferably 20:80 to 80:20, based on the molar ratio of formula (I): formula (II).

[0345] The monomer (b2) is preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group.

[0346] Preferred examples of the monomer (b2) include 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, 3-methyl-3-(meth)acryloyloxyethyloxetane and 3-ethyl-3-(meth)acryloyloxyethyloxetane.

[0347] The monomer (b3) is preferably a monomer having a tetrahydrofuranyl group and a (meth)acryloyloxy group. Preferred examples of the monomer (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

[0348] Specific examples of the monomer (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0](meth)acrylate, 2,6 ] decane-8-yl ester (in the technical field, it is commonly known as "dicyclopentyl (meth)acrylate". It is also sometimes called "tricyclodecyl (meth)acrylate"), tricyclo[5.2.1.0 2,6] (meth)acrylates such as decen-8-yl ester (in the technical field, it is commonly referred to as "dicyclopentenyl (meth)acrylate"), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate and benzyl (meth)acrylate;

[0349] (Meth)acrylates containing a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

[0350] Diethyl maleate, diethyl fumarate, diethyl itaconate and other dicarboxylic acid diesters;

[0351] Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxy Bicyclic unsaturated compounds such as bicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene;

[0352] 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;

[0353] Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

[0354] Among them, from the viewpoint of copolymerization reactivity and heat resistance, as (c), benzyl (meth)acrylate, tricyclodecyl (meth)acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, etc. are preferred. In addition, benzyl (meth)acrylate and tricyclodecyl (meth)acrylate are more preferred as (c) because of their excellent developability during pattern formation.

[0355] In the resin [K1], the ratio of the structural unit derived from each unit in all the structural units constituting the resin [K1] is preferably in the following range.

[0356] Structural units derived from monomer (a): preferably 2 mol% to 50 mol% (more preferably 10 mol% to 45 mol%),

[0357] The content of the structural units derived from the monomer (b), particularly the structural units derived from the monomer (b1) is preferably 50 mol% to 98 mol% (more preferably 55 mol% to 90 mol%).

[0358] When the ratio of the structural unit of the resin [K1] is within the above range, there is a tendency for the storage stability, developability, and solvent resistance of the obtained pattern to be excellent.

[0359] The resin [K1] can be produced by referring to the method described in the document "Experimental Methods for Polymer Synthesis" (Otsu Takayuki, Kagaku Dojin, 1st edition, 1st printing, published on March 1, 1972) and the references described in the document.

[0360] Specifically, the following method can be cited: a specified amount of monomer (a) and monomer (b) (especially monomer (b1)), a polymerization initiator and a solvent are charged into a reaction container, and stirred, heated and kept warm in a deoxygenated atmosphere. It should be noted that the polymerization initiator and solvent used here are not particularly limited, and polymerization initiators and solvents commonly used in this field can be used. As polymerization initiators, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile) etc.) and organic peroxides (benzoyl peroxide etc.) can be cited. As a solvent, any solvent that dissolves each monomer can be used, and a solvent (E) described later as a solvent for a colored curable resin composition can be used.

[0361] The obtained copolymer may be used directly as a solution after the reaction, or as a solution after concentration or dilution, or as a solid (powder) obtained by reprecipitation, etc. In particular, by using a solvent (E) described later as a solvent during the polymerization, the solution after the reaction can be used directly, and the production process can be simplified.

[0362] In the resin [K2], the ratio of the structural unit derived from each unit in all the structural units constituting the resin [K2] is preferably in the following range.

[0363] Structural units derived from monomer (a): preferably 4 mol% to 45 mol% (more preferably 10 mol% to 30 mol%),

[0364] The structural unit derived from the monomer (b), in particular the structural unit derived from the monomer (b1): preferably 2 mol% to 95 mol% (more preferably 5 mol% to 80 mol%),

[0365] Structural unit derived from monomer (c): preferably 1 mol% to 65 mol% (more preferably 5 mol% to 60 mol%).

[0366] When the ratio of the structural unit of the resin [K2] is within the above range, there is a tendency for the storage stability, developability, solvent resistance, heat resistance, and mechanical strength of the obtained pattern to be excellent.

[0367] Resin [K2] can be produced in the same manner as described as the method for producing resin [K1]. Specifically, the following method can be mentioned: a predetermined amount of monomer (a), monomer (b) (particularly monomer (b1)) and monomer (c), a polymerization initiator and a solvent are placed in a reaction vessel, and stirred, heated and kept warm in a deoxygenated atmosphere. The obtained copolymer may be used as a solution after the reaction, or may be used as a concentrated or diluted solution, or may be used as a substance taken out in a solid (powder) form by a method such as reprecipitation.

[0368] In the resin [K3], the ratio of the structural unit derived from each unit in all the structural units constituting the resin [K3] is preferably in the following range.

[0369] Structural units derived from monomer (a): preferably 2 mol% to 55 mol% (more preferably 10 mol% to 50 mol%),

[0370] Structural unit derived from monomer (c): preferably 45 mol% to 98 mol% (more preferably 50 mol% to 90 mol%).

[0371] The resin [K3] can be produced in the same manner as described as the method for producing the resin [K1].

[0372] Resin [K4] can be produced by obtaining a copolymer of monomer (a) and monomer (c), and adding a cyclic ether structure having 2 to 4 carbon atoms in monomer (b), especially an oxirane ring in monomer (b1), to a carboxylic acid and / or a carboxylic anhydride in monomer (a). Specifically, first, a copolymer of monomer (a) and monomer (c) is produced in the same manner as described as a method for producing resin [K1]. In this case, the ratio of the structural unit derived from each unit is preferably in the following range among all the structural units constituting the copolymer of monomer (a) and monomer (c).

[0373] Structural units derived from monomer (a): preferably 5 mol% to 50 mol% (more preferably 10 mol% to 45 mol%),

[0374] Structural unit derived from monomer (c): preferably 50 mol% to 95 mol% (more preferably 55 mol% to 90 mol%).

[0375] Next, the cyclic ether structure having 2 to 4 carbon atoms of the monomer (b), in particular the oxirane ring of the monomer (b1), is reacted with a portion of the carboxylic acid and / or carboxylic anhydride derived from the monomer (a) in the above copolymer. Specifically, after the copolymer of the monomer (a) and the monomer (c) is produced, the atmosphere in the flask is replaced from nitrogen to air, and the monomer (b) (in particular the monomer (b1)), the carboxylic acid or the carboxylic anhydride, the reaction catalyst of the cyclic ether structure (for example, tris(dimethylaminomethyl)phenol, etc.), and the polymerization inhibitor (for example, hydroquinone, etc.) are placed in the flask and reacted at 60 to 130° C. for 1 to 10 hours, thereby obtaining the resin [K4].

[0376] The amount of monomer (b), especially monomer (b1), used is preferably 5 to 80 mol, more preferably 10 to 75 mol, relative to 100 mol of monomer (a). Within this range, there is a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity to become good. In view of the high reactivity of the cyclic ether structure and the difficulty in residual unreacted monomer (b), the monomer (b) used in the resin [K4] is preferably monomer (b1), and more preferably monomer (b1-1).

[0377] The amount of the reaction catalyst used is preferably 0.001% to 5% by mass relative to the total amount of the monomer (a), the monomer (b) (particularly the monomer (b1)) and the monomer (c). The amount of the polymerization inhibitor used is preferably 0.001% to 5% by mass relative to the total amount of the monomer (a), the monomer (b) and the monomer (c).

[0378] The reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the heat generated by polymerization, etc. It should be noted that the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the heat generated by polymerization, etc., similarly to the polymerization conditions.

[0379] As for resin [K5], as the first stage, a copolymer of monomer (b) (particularly monomer (b1)) and monomer (c) is obtained in the same manner as in the production method of resin [K1]. As in the above, the obtained copolymer may be used directly as a solution after the reaction, or may be used after a concentration or dilution, or may be used after being taken out in a solid (powder) form by a method such as reprecipitation.

[0380] The ratio of the structural units derived from the monomer (b) (particularly the monomer (b1)) and the monomer (c) relative to the total number of moles of all structural units constituting the above copolymer is preferably in the following range.

[0381] The structural unit derived from the monomer (b), in particular the structural unit derived from the monomer (b1): preferably 5 mol% to 95 mol% (more preferably 10 mol% to 90 mol%),

[0382] Structural unit derived from monomer (c): preferably 5 mol% to 95 mol% (more preferably 10 mol% to 90 mol%).

[0383] Furthermore, under the same conditions as the method for producing resin [K4], the carboxylic acid or carboxylic anhydride contained in monomer (a) is reacted with the cyclic ether structure contained in the copolymer of monomer (b) (particularly monomer (b1)) and monomer (c) and derived from monomer (b), thereby obtaining resin [K5]. The amount of monomer (a) to be reacted with the above copolymer is preferably 5 to 80 mol relative to 100 mol of monomer (b) (particularly monomer (b1)). In view of the high reactivity of the cyclic ether structure and the difficulty in the unreacted monomer (b) remaining, the monomer (b) used in resin [K5] is preferably monomer (b1), and more preferably monomer (b1-1).

[0384] The resin [K6] is a resin obtained by further reacting the resin [K5] with a carboxylic anhydride. The hydroxyl group generated by the reaction of the cyclic ether structure with the carboxylic acid or the carboxylic anhydride is reacted with the carboxylic anhydride.

[0385] Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (nadic anhydride).

[0386] Among the resins [K1] to [K6], the preferred resin as the resin (B) is [K1] or [K2]. The resin (B) may be composed of one type of resin or may contain two or more types of resins.

[0387] The weight average molecular weight (Mw) of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. When the weight average molecular weight (Mw) is within the above range, the solubility of the unexposed portion in the developer is high, and the residual film rate and hardness of the obtained pattern tend to be high. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

[0388] The acid value of the resin (B) in terms of solid content is preferably 5 mg-KOH / g to 200 mg-KOH / g, more preferably 50 mg-KOH / g to 180 mg-KOH / g, and even more preferably 60 mg-KOH / g to 140 mg-KOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined, for example, by titration using a potassium hydroxide aqueous solution.

[0389] The content of the resin (B) is preferably 1% to 65% by mass, more preferably 3% to 60% by mass, and further preferably 5% to 55% by mass in the solid content of the colored curable resin composition. When the content of the resin (B) is within the above range, a colored pattern can be formed, and there is a tendency for the resolution and residual film rate of the colored pattern to be improved.

[0390] After the liquid containing the colorant is prepared in advance, when the liquid containing the colorant is used to prepare the colored curable resin composition, the liquid containing the colorant may contain a part or all, preferably a part, of the resin (B) described below contained in the colored curable resin composition. The dispersion stability of the liquid containing the colorant can be further improved by containing the resin (B) in advance. It is preferred that the liquid containing the colorant contains the resin (B2) in advance.

[0391] The content of the resin (B) in the colorant-containing liquid may be, for example, 10,000 parts by mass or less, preferably 5,000 parts by mass or less, more preferably 1,000 parts by mass or less, further preferably 1 to 500 parts by mass, particularly preferably 5 to 200 parts by mass, and particularly preferably 10 to 100 parts by mass, relative to 100 parts by mass of the colorant (A).

[0392] 〔3〕Polymerizable compound (C)

[0393] The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by active free radicals generated by the polymerization initiator (D) by light irradiation or the like, and examples thereof include compounds having polymerizable ethylenically unsaturated bonds (preferably (meth)acrylate compounds). The weight average molecular weight of the polymerizable compound (C) is preferably 3000 or less, and more preferably 1500 or less. In addition, the lower limit of the weight average molecular weight of the polymerizable compound (C) may be 50 or more, or 150 or more.

[0394] Among them, the polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds, and examples thereof include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, and tetrapentaerythritol deca(meth)acrylate. acrylate, pentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc. Among them, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are preferred.

[0395] The colored curable resin composition of the present invention may contain one or more polymerizable compounds (C). The content of the polymerizable compound (C) is preferably 20 to 150 parts by mass, and more preferably 40 to 110 parts by mass, relative to 100 parts by mass of the resin (B) in the colored curable resin composition.

[0396] The content of the polymerizable compound (C) is preferably 1% to 65% by mass, more preferably 3% to 60% by mass, and further preferably 5% to 55% by mass relative to the total amount of the solid component. When the content of the polymerizable compound (C) is within the above range, there is a tendency for the residual film rate during color pattern formation and the chemical resistance of the color filter to be improved.

[0397] 〔4〕Polymerization initiator (D)

[0398] The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. under the action of light or heat to initiate polymerization, and a known polymerization initiator can be used.

[0399] Examples of the polymerization initiator (D) include oxime compounds such as O-acyl oxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.

[0400] Two or more polymerization initiators (D) may be used in combination in consideration of sensitivity, formation of a precise pattern shape, etc. The polymerization initiator (D) preferably contains an oxime compound such as an O-acyl oxime compound because it is advantageous in terms of sensitivity and precise formation of a pattern shape having a desired line width.

[0401] The O-acyl oxime compound is a compound having a structure represented by formula (d). Hereinafter, * represents a bonding site.

[0402]

[0403] Examples of such 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-carbazole-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolanylmethoxy)benzoyl}-9H-carbazole-3-yl]ethane-1-imine, The O-acyl oxime compound is preferably selected from at least one of N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine and N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine. Commercially available products such as Irgacure OXE01, OXE02, and OXE03 (all manufactured by BASF Corporation) and N-1919 (manufactured by ADEKA Corporation) may also be used. When these O-acyl oxime compounds are used, a color filter having excellent lithographic performance tends to be obtained.

[0404] The alkylphenone compound is a compound having a structure represented by formula (d4) or a structure represented by formula (d5). * represents a bonding site. In these structures, the benzene ring may have a substituent.

[0405]

[0406] Examples of the compound having a structure represented by formula (d4) include 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]butane-1-one. Commercially available products such as Irgacure 369, 907, and 379 (all manufactured by BASF Corporation) can also be used.

[0407] Examples of the compound having a structure represented by formula (d5) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, and benzil dimethyl ketal.

[0408] In terms of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by formula (d4).

[0409] 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 (for example, see Japanese Patent Application Laid-Open Nos. 6-75372 and 6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, Biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboalkoxy groups (for example, see Japanese Patent Publication No. 7-10913). Among them, compounds represented by the following formula or mixtures thereof are preferred.

[0410]

[0411] 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-[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, and the like.

[0412] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0413] In addition, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl benzoylformate, and titanocene compounds, etc. These are preferably used in combination with the polymerization initiator aid (D1) (particularly amines) described later.

[0414] The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 2 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, there is a tendency for high sensitivity and shortened exposure time, and thus there is a tendency for improved productivity of the color filter.

[0415] 〔5〕Polymerization initiator aid (D1)

[0416] The polymerization initiator aid (D1) is a compound or a sensitizer for accelerating the polymerization of the polymerizable compound that is initiated to polymerize by the polymerization initiator. When the polymerization initiator aid (D1) is included, it is used in combination with the polymerization initiator (D).

[0417] Examples of the polymerization initiator aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds. Among them, thioxanthone compounds are preferred. Two or more polymerization initiator aids (D1) may be used in combination.

[0418] Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isopentyl 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. Among them, 4,4'-bis(diethylamino)benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may also be used.

[0419] 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.

[0420] Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0421] 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.

[0422] The content of the polymerization initiator aid (D1) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator aid (D1) is within the above range, a blue pattern can be formed with higher sensitivity, and there is a tendency for the productivity of the color filter to be improved.

[0423] 〔6〕Solvent (E)

[0424] The colored curable resin composition of the present invention contains a solvent (also referred to as solvent (E)). In the present invention, the solvent contains at least an alkanediol diacetate having 4 to 6 carbon atoms and an alkyl ester of acetic acid having 2 to 4 carbon atoms.

[0425] Examples of the alkanediol diacetate having 4 to 6 carbon atoms include butanediol diacetate (also referred to as butanediol diacetate), pentanediol diacetate, and hexanediol diacetate. Examples of the butanediol diacetate include 1,2-butanediol diacetate, 1,3-butanediol diacetate, 1,4-butanediol diacetate, and 2,3-butanediol diacetate, preferably 1,3-butanediol diacetate and 1,4-butanediol diacetate, and particularly preferably 1,4-butanediol diacetate.

[0426] The content of the alkane diol diacetate having 4 to 6 carbon atoms is 1% to 20% by mass in 100% by mass of the solvent, preferably 1.5% to 18% by mass, more preferably 2% to 16% by mass, and further preferably 2.5% to 14% by mass. When it is in the above range, even after the colored curable resin composition is applied to the substrate, a certain fluidity can be ensured, and the amount of adhesion of the colored coating film can be reduced. When the content of the alkane diol diacetate having 4 to 6 carbon atoms is too high, there is a tendency that the curing of the colored curable resin composition becomes insufficient. Therefore, in the development process of the manufacturing method of the color filter described later, since all or part of the pattern is dissolved in the developer, the desired colored coating film or colored pattern is sometimes not obtained.

[0427] The alkanediol diacetate may be a high boiling point solvent, and the boiling point of the alkanediol diacetate is preferably higher than 150°C and lower than 300°C, more preferably higher than 160°C, further preferably higher than 170°C, further preferably higher than 180°C, and particularly preferably higher than 190°C.

[0428] Examples of the alkyl ester of acetic acid having 2 to 4 carbon atoms include ethyl acetate, propyl acetate, n-butyl acetate, isobutyl acetate, and the like.

[0429] Among them, the alkyl ester of acetic acid having 2 to 4 carbon atoms is more preferably n-butyl acetate and isobutyl acetate, and n-butyl acetate is particularly preferred.

[0430] The content of the alkyl ester of acetic acid having 2 to 4 carbon atoms is preferably 1% to 97% by mass, more preferably 2% to 95% by mass, further preferably 3% to 93% by mass, and further preferably 5% to 90% by mass in 100% by mass of the solvent. The content of the alkyl ester of acetic acid having 2 to 4 carbon atoms may be 45% by mass or more, 50% by mass or more, or 60% by mass or more in 100% by mass of the solvent.

[0431] The content ratio of the alkanediol diacetate having 4 to 6 carbon atoms / the alkyl ester of acetic acid having 2 to 4 carbon atoms is preferably 0.02 to 1.0, more preferably 0.03 to 0.8, further preferably 0.04 to 0.7, and further preferably 0.05 to 0.5. Within the above range, even if the colorant concentration in the colored curable resin composition is increased, the amount of the colored coating film can be reduced.

[0432] As described later, the solvent preferably further contains an ether ester solvent having a boiling point of 150° C. or lower.

[0433] The solvent (E) may contain the following solvents as other solvents. Examples of other solvents (E) include ester solvents (solvents containing -COO-), ether solvents other than ester solvents (solvents containing -O-), ether ester solvents (solvents containing -COO- and -O-), ketone solvents other than ester solvents (solvents containing -CO-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

[0434] Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, 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.

[0435] 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-dihydrofu ... 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.

[0436] 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.

[0437] The ether ester solvent having a boiling point of 150° C. or lower is preferably propylene glycol monomethyl ether acetate or ethylene glycol monomethyl ether acetate, and particularly preferably propylene glycol monomethyl ether acetate.

[0438] 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.

[0439] Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene. Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0440] The content of other solvents (E) (preferably ether ester solvents, more preferably propylene glycol monomethyl ether acetate) in 100% by mass of the solvent (E) is preferably 1% by mass to 80% by mass, more preferably 1% by mass to 70% by mass, further preferably 2% by mass to 60% by mass, and further preferably 50% by mass or less or 40% by mass or less.

[0441] The content of the solvent (E) is preferably 70% to 95% by mass, more preferably 75% to 92% by mass in the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5% to 30% by mass, more preferably 8% to 25% by mass. When the content of the solvent (E) is within the above range, the flatness during coating becomes good, and the color concentration is not insufficient when forming a color filter, so there is a tendency for the display characteristics to become good.

[0442] 〔7〕Leveling agent (F)

[0443] The colored curable resin composition of the present invention may contain one or more leveling agents (F). As the leveling agent (F), there may be mentioned silicone surfactants (without fluorine atoms), fluorine surfactants, and silicone surfactants having fluorine atoms. These may have polymerizable groups in the side chains.

[0444] Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specific examples include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.).

[0445] Examples of the fluorine-based surfactant include surfactants having a fluorine carbon chain in the molecule. Specifically, examples include FLUORAD (registered trademark) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemicals Laboratories, Ltd.), etc.

[0446] Examples of the organosilicon-based surfactant having a fluorine atom 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).

[0447] The content of the leveling agent (F) in the colored curable resin composition is usually 0.001 to 0.6 mass%, preferably 0.002 to 0.4 mass%, and more preferably 0.005 to 0.3 mass%. This content does not include the content of the pigment dispersant.

[0448] 〔8〕Other ingredients

[0449] The colored curable resin composition of the present invention may contain one or more additives such as a filler, a polymer compound other than the resin (B), an adhesion promoter, an ultraviolet absorber, an antioxidant, an anti-agglomeration agent, an organic acid, an organic amine compound, and a curing agent as needed.

[0450] <Method for producing colored curable resin composition>

[0451] 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), a solvent (E), and, if necessary, a leveling agent (F), a polymerization initiator aid (D1), and other components.

[0452] <Color filter, method for manufacturing the same, and display element>

[0453] The colored curable resin composition of the present invention is useful as a material for a color filter. A color filter formed from the colored curable resin composition of the present invention also belongs to the scope of the present invention. The color filter may also be formed into a colored pattern.

[0454] As a method for manufacturing a colored pattern by the colored curable resin composition of the present invention, photolithography, inkjet method, printing method, etc. can be cited, and photolithography can be preferably cited. Photolithography is a method of applying a colored curable resin composition to a substrate to dry it to form a colored composition layer, and exposing the colored composition layer through a photomask and developing it. In the photolithography, a colored coating film as a cured product of the above-mentioned colored composition layer can be formed without using a photomask and / or developing during exposure. The colored pattern and colored coating film formed by the colored curable resin composition of the present invention are the color filter of the present invention. The color filter of the present invention is typically used as a colored pixel.

[0455] As the substrate, quartz glass, borosilicate glass, aluminosilicate glass, glass plates such as soda-lime glass coated with silicon dioxide on the surface, resin plates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, and substrates on which aluminum, silver, silver / copper / palladium alloy thin films are formed can be used. Other color filter layers, resin layers, transistors, circuits, etc. can be formed on these substrates. In addition, a substrate treated with HMDS (1,1,1,3,3,3-hexamethyldisilazane) on a silicon substrate can also be used.

[0456] The formation of each colored pixel based on the photolithography method can be carried out using a known or customary device and condition. For example, it can be produced as described below. First, the colored curable resin composition is applied to the substrate, and heated and dried (pre-baked) and / or dried under reduced pressure, thereby removing volatile components such as solvents and drying to obtain a smooth colored composition layer. As a coating method, a spin coating method, a slit coating method, and a slit spin coating method can be cited.

[0457] The temperature for heat drying is preferably 30 to 120° C., more preferably 50 to 110° C. In addition, the heating time is preferably 10 seconds to 5 minutes, more preferably 30 seconds to 3 minutes. When the reduced pressure drying is performed, it is preferably carried out at a pressure of 50 to 150 Pa and a temperature range of 20 to 25° C. The thickness of the coloring composition layer is not particularly limited and can be appropriately selected according to the thickness of the target color filter.

[0458] Next, the colored composition layer is exposed through a photomask for forming a target colored pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the target application is used. As the light source used for exposure, a light source that generates light with a wavelength of 250 to 450 nm is preferably used. For example, light less than 350 nm can be cut off using a filter that cuts off the 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, as light sources, mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, etc. can be cited.

[0459] In order to uniformly irradiate the entire exposure surface with parallel light and accurately align the photomask and the substrate on which the colored composition layer is formed, it is preferred to use an exposure device such as a mask aligner (close-up exposure machine) and a stepper (reduction projection exposure machine) for exposure.

[0460] The exposed colored composition layer is brought into contact with a developer to be developed, thereby forming a colored coating film (colored pattern) on the substrate. The unexposed portion of the colored composition layer is dissolved in the developer and removed by the development.

[0461] The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide. The concentration of the aqueous solution of these alkaline compounds is preferably 0.01% to 10% by mass, more preferably 0.03% to 5% by mass. In addition, the developer may contain a surfactant.

[0462] The developing method may be any of a paddle method, an immersion method, a spray method, etc. Furthermore, the substrate may be tilted at an arbitrary angle during the developing process. After the developing process, water washing is preferably performed.

[0463] The obtained colored pattern is preferably further post-baked. The post-baking temperature is preferably 80°C to 250°C, more preferably 100°C to 250°C, further preferably 150°C to 250°C, and further preferably 160°C to 235°C. The post-baking time is preferably 1 minute to 120 minutes, more preferably 2 minutes to 120 minutes, further preferably 10 minutes to 60 minutes, and further preferably 10 minutes to 30 minutes.

[0464] Since the thickness of the obtained colored pattern affects adjacent pixels, it is preferably as thin as possible. In particular, in the case of a thick film, when a liquid crystal panel is made, the light from the light source sometimes leaks through pixels of more than 2 colors, and when the panel is observed from an oblique direction, the vividness of the color may be lost. The thickness of the colored pattern after post-baking is generally preferably less than 3 μm, more preferably less than 2.8 μm, and further preferably less than 2.5 μm. The lower limit of the thickness of the colored pattern is not particularly limited, and is usually more than 0.1 μm, preferably more than 0.2 μm, and may also be more than 0.5 μm or more than 1.0 μm. The colored curable resin composition of the present invention is excellent in developing properties when the colored pattern is manufactured, and is therefore excellent as a material for a color filter.

[0465] The colored coating film formed from the colored curable resin composition of the present invention is a color filter formed by forming a pattern on a substrate and partially overlapping with a black matrix, and the adhesion rate represented by the ratio of the thickness (a) of the color filter on the black matrix to the thickness (b) of the color filter on the substrate [(a) / (b)] is 0.71 or less.

[0466] Figure 1 In FIG. 1 , the color filter 1 is composed of a substrate 3 , a black matrix 2 , and each color pixel (not shown), and the adhesion rate is defined by the following formula.

[0467] Color filter adhesion rate = [thickness of color filter on black matrix (a)] / [thickness of color filter on substrate (b)]

[0468] In the present specification, the adhesion rate can be defined as a value measured for a colored coating film initially formed on a substrate.

[0469] The thickness of the color filter refers to the maximum thickness of the color filter from the substrate or the maximum thickness of the color filter from the black matrix when the color filter is patterned to have a concavo-convex shape or a tapered shape.

[0470] The adhesion rate represented by the ratio of the thickness (a) of the color filter on the black matrix to the thickness (b) of the color filter on the substrate [(a) / (b)] is, for example, less than 0.75, preferably less than 0.74, more preferably less than 0.73, further preferably less than 0.72, further preferably less than 0.71, for example greater than 0, and greater than 0.01 or greater than 0.1.

[0471] The color filter of the present invention is useful as a color filter used in display elements such as liquid crystal display elements, organic EL elements, electronic paper, etc., and solid-state imaging elements.

[0472] Example

[0473] Hereinafter, the curable resin composition of the present invention will be described with reference to specific examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, "parts" represent "parts by mass" and "%" represents "% by mass". In addition, unless otherwise specified, the reaction is carried out under a nitrogen atmosphere.

[0474] Hereinafter, the structures of the compounds were confirmed by mass spectrometry (LC; Model 1200 manufactured by Agilent, MASS; Model LC / MSD manufactured by Agilent).

[0475] The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.

[0476] Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)

[0477] Column: TSK-GELG2000HXL

[0478] Column temperature: 40°C

[0479] Solvent: THF

[0480] Flow rate: 1.0mL / min

[0481] Solid content concentration of test liquid: 0.001 to 0.01 mass%

[0482] Injection volume: 50 μL

[0483] Detector: RI

[0484] Calibration standard substances: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

[0485] The ratio of the polystyrene-equivalent weight average molecular weight to the number average molecular weight (Mw / Mn) obtained above was defined as the degree of dispersion (molecular weight distribution).

[0486] The acid value of the resin in terms of solid content is a value obtained by titrating a solution containing the resin with an aqueous potassium hydroxide solution to determine the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin.

[0487] Method for measuring adhesion ratio [thickness on line pattern (a) / thickness on substrate (b)]

[0488] The colored curable resin composition was applied by spin coating to a surface having a line pattern of 2.0 μm in thickness (equivalent to Figure 1 The 2-inch square glass substrate (EAGLE 2000; manufactured by CORNING) with a black matrix was then pre-baked at 100°C for 3 minutes to form a colored composition layer. After cooling, an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) was used to expose the 2-inch square glass substrate (EAGLE 2000; manufactured by CORNING) in an atmospheric atmosphere at 20 mJ / cm 2 The colored composition layer was irradiated with light at an exposure amount (365 nm basis). After the light irradiation, the colored coating film was post-baked in an oven at 230° C. for 30 minutes to obtain a colored coating film. After cooling, the thickness of the obtained colored coating film on the glass substrate and on the line pattern was measured using a thickness measuring device (DEKTAK3; manufactured by Japan Vacuum Technology Co., Ltd.). The thickness of the colored coating film on the line pattern is the value obtained by subtracting the thickness of the line pattern from the thickness from the substrate to the outermost surface of the colored coating film, which is set as (a). In addition, the thickness of the colored coating film on the substrate is the thickness of the colored coating film on the glass substrate, which is set as (b), and the adhesion rate is calculated.

[0489] [Synthesis example 1]

[0490] An appropriate amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen, and 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80°C while stirring. Then, 38 parts of acrylic acid and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decane-8-yl ester and 3,4-epoxytricyclic acrylate [5.2.1.0 2 ,6] A mixed solution of 289 parts of a mixture of decane-9-yl ester (containing a ratio of 1:1 in molar ratio) and 125 parts of propylene glycol monomethyl ether acetate. On the other hand, a solution prepared by dissolving 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the addition was completed, the mixture was kept at 80°C for 4 hours and then cooled to room temperature to obtain a copolymer (resin B1) solution having a solid content of 35.1% and a viscosity of 125 mPa·s measured by a B-type viscometer (23°C). The weight average molecular weight Mw of the resulting copolymer was 9.2×10 3 , a dispersion degree (molecular weight distribution) of 2.08, and an acid value converted to solid content of 77 mg-KOH / g. The resin (B1) has the following structural units.

[0491]

[0492] [Preparation of dispersion liquid]

[0493] As the dispersion 1, a dispersion containing the following components was used.

[0494] (Dispersion 1)

[0495] A dispersion having a solid content of 21.5% containing 4.8 parts of CI Pigment Red 291 (bromide diketopyrrolopyrrole), 13.6 parts of CI Pigment Red 177, 2.1 parts of CI Pigment Yellow 150, 6.4 parts of an acrylic dispersant (based on solid content), 7.9 parts of an acrylic resin (based on solid content), and 126.9 parts of propylene glycol monomethyl ether acetate.

[0496] (Dispersion 2)

[0497] A dispersion having a solid content of 22.7% containing 0.9 parts of CI Pigment Yellow 150, 5.5 parts of CI Pigment Green 58, 1.2 parts of an acrylic dispersant (based on solid content), 2.5 parts of an acrylic resin (based on solid content), and 34.3 parts of propylene glycol monomethyl ether acetate.

[0498] (Dispersion 3)

[0499] A dispersion having a solid content of 25.4% containing 4.3 parts of CI Pigment Blue 15:6, 0.5 parts of a compound represented by formula (1-32), 1.3 parts of an acrylic dispersant (based on solid content), 1.0 parts of an acrylic resin (based on solid content), and 20.9 parts of propylene glycol monomethyl ether acetate.

[0500] [Examples 1 to 3, Comparative Examples 1 to 6]

[0501] [Preparation of colored curable resin composition]

[0502] Each component shown in Table 2 was mixed to obtain each colored curable resin composition.

[0503] Colorant (A): Dispersions 1 to 3 (the values ​​in the table are the amounts of the dispersions used)

[0504] · Resin (B): Use resin (B1) (The values ​​in the table are based on solid content)

[0505] ·Polymerizable compound (C)

[0506] (C-1): dipentaerythritol polyacrylate (A-9550APHA; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0507] Polymerization initiator (D):

[0508] (D-1): Irgacure (registered trademark) OXE-03; manufactured by BASF; compound represented by formula (d1-40)

[0509]

[0510] Solvent (E):

[0511] (E-1): Propylene glycol monomethyl ether acetate (hereinafter also referred to as PGMA)

[0512] (E-2): 1,4-Butanediol diacetate (hereinafter also referred to as 1,4-BGDA)

[0513] (E-3): Butyl acetate (hereinafter also referred to as BA)

[0514] Leveling agent (F):

[0515] (F-1): Polyether modified silicone oil (solid content conversion)

[0516] (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.)

[0517] [Table 2]

[0518]

[0519] About the obtained colored curable resin composition, the color filter was formed by the following method, and the evaluation was performed.

[0520] <Formation of color filter (colored coating film)>

[0521] The colored curable resin composition was applied by spin coating on a 2-inch square glass substrate (EAGLE 2000; manufactured by CORNING) with a line pattern of 2.0 μm in thickness, and then pre-baked at 100°C for 3 minutes to form a colored composition layer. After cooling, an exposure machine (TME-150RSK; manufactured by TOPCON Corporation) was used to expose the colored composition layer at 20 mJ / cm in air atmosphere. 2 The colored composition layer was irradiated with light at an exposure amount (365 nm reference). After the light irradiation, the colored coating film was post-baked at 230° C. for 30 minutes in an oven. After cooling, the thickness of the obtained colored coating film on the glass substrate and on the line pattern was measured using a thickness measuring device (DEKTAK3; manufactured by Japan Vacuum Technology Co., Ltd.). The thickness and adhesion rate of the colored coating film are shown in Table 3.

[0522] [Table 3]

[0523]

[0524] In Examples 1 to 3, the adhesion rate was lower than that in Comparative Examples 1 to 6. Therefore, when a color filter or the like is produced from the colored curable resin composition of the present invention, an improvement in the yield can be expected.

[0525] Industrial Applicability

[0526] The colored curable resin composition of the present invention can form a colored coating film with a reduced adhesion rate, and the yield of color filters, display devices, solid-state imaging elements, etc. is improved, so it is extremely useful industrially.

[0527] Explanation of symbols

[0528] 1: Color Filter

[0529] 2: Black Matrix

[0530] 3: Substrate

[0531] a: Thickness of the color filter on the black matrix

[0532] b: Thickness of the color filter on the substrate

Claims

1. A colored curable resin composition, characterized in that Contains a colorant, a resin, a polymerizable compound, a polymerization initiator and a solvent, The solvent contains at least an alkanediol diacetate having 4 to 6 carbon atoms and an alkyl ester of acetic acid having 2 to 4 carbon atoms. The solvent further comprises an ether ester solvent having a boiling point below 150°C, The content of the alkanediol diacetate having 4 to 6 carbon atoms is 1 to 20% by mass in 100% by mass of the solvent, and the content of the alkyl ester of acetic acid having 2 to 4 carbon atoms is 1 to 97% by mass in 100% by mass of the solvent.

2. The colored curable resin composition according to claim 1, wherein The content of the ether ester solvent having a boiling point of 150° C. or less is 1% by mass to 80% by mass in 100% by mass of the solvent.

3. The colored curable resin composition according to claim 1, wherein The content ratio of the alkanediol diacetate having 4 to 6 carbon atoms to the alkyl ester of acetic acid having 2 to 4 carbon atoms is 0.02 to 1.

0.

4. The colored curable resin composition according to claim 1, wherein The content of the colorant is 10% by mass to 55% by mass in 100% by mass of the solid content of the colored curable resin composition, and the colorant includes one or more selected from the group consisting of a red pigment, a green pigment, and a blue pigment. 5 . A color filter formed from the colored curable resin composition according to claim 1 . A display device comprising the color filter according to claim 5 . 7 . A solid-state imaging element comprising the color filter according to claim 5 .

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