CN114207523A - Colored curable resin composition - Google Patents

Abstract

A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator and a solvent, wherein the solvent comprises at least C4-C6 alkanediol diacetate and C2-C4 alkyl acetate, and the content of the C4-C6 alkanediol diacetate is 1 to 20% by mass based on 100% by mass of the solvent.

Description

Colored curable resin composition

Technical Field

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

Background

As a colored curable resin composition for forming a color filter included in a display device, a solid-state imaging element, or the like, a colored curable resin composition including a colorant, a binder resin, a polymerizable compound, a polymerization initiator, and a solvent is known (patent documents 1 and 2).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2009 + 091551

Patent document 2: japanese patent application laid-open No. 2010-044285

Disclosure of Invention

The color filter includes a substrate, colored pixels, a black matrix formed on the substrate and separating the colored pixels from each other, and the like.

From the viewpoint of preventing light leakage, the end portions of the respective colored pixels are usually formed so as to overlap the black matrix, and on the other hand, if the colorant concentration is increased in a color filter requiring high color reproducibility, the colored coating film of the respective colored pixels present on the black matrix tends to form a bulge, and it is desired to reduce the amount of adhesion of the colored coating film on the black matrix (hereinafter also referred to as an adhesion rate (on り)).

The purpose of the present invention is to provide a colored curable resin composition capable of forming a colored coating film having a reduced rate of adhesion of the colored coating film on a black matrix.

The invention provides a colored curable resin composition, a color filter, a display device and a solid-state imaging element shown below.

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

the solvent at least contains C4-6 alkane diol diacetate and C2-4 alkyl ester of acetic acid,

the content of the C4-6 alkanediol diacetate is 1 to 20% by mass based on 100% by mass of the solvent.

[2] The colored curable resin composition according to [1], wherein the content ratio of the C4-6 alkanediol diacetate to the C2-4 alkyl ester of acetic acid is 0.02-1.0.

[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 ℃ or lower.

[4] The colored curable resin composition according to any one of [1] to [3], wherein the content of the colorant is 10 to 55% by mass based on 100% by mass of the solid content of the colored curable resin composition, and the colorant contains 1 or more selected from a red pigment, a green pigment and a blue pigment.

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

[6] A color filter formed by forming a pattern on a substrate and partially overlapping a black matrix, wherein 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 indicates an adhesion ratio of 0.71 or less.

[7] A display device comprising the color filter of [5] or [6 ].

[8] A solid-state imaging element comprising the color filter according to [5] or [6 ].

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

In addition, 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.

Drawings

Fig. 1 is a graph showing the adhesion rate expressed 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

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)).

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)).

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

[1] coloring agent (A)

The colored curable resin composition of the present invention contains a colorant (a). The colorant (a) preferably contains at least 1 selected from a dye and a pigment, and more preferably contains a pigment. The colorant (a) may contain 1 or 2 or more.

[ pigment ]

Examples of The pigment include organic pigments and inorganic pigments, and examples thereof include compounds classified as pigments in The color index (published by The Society of Dyers and Colourists). The pigments may be used alone or in combination of 2 or more.

Examples of the pigment include yellow pigments such as c.i. 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, 214;

orange pigments such as c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

red pigments such as c.i. 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 the like;

c.i. pigment blue 15, 15:3, 15:4, 15:6, 60, etc.;

c.i. pigment violet 1, 19, 23, 29, 32, 36, 38 and the like violet pigment;

green pigments such as c.i. pigment green 7, 36, 58, 59;

c.i. brown pigments such as pigment brown 23, 25;

and black pigments such as c.i. pigment black 1 and 7.

The pigment may be subjected to rosin treatment, surface treatment using a pigment derivative or the like into which an acidic group or a basic group has been introduced, grafting treatment on the surface of the pigment using a polymer compound or the like, micronization treatment using a sulfuric acid micronization method or the like, cleaning treatment using an organic solvent, water or the like for removing impurities, removal treatment using an ion exchange method or the like for removing ionic impurities, or the like, as required. The particle diameters of the pigments are preferably uniform.

The pigment may be dispersed by including a pigment dispersant to prepare a pigment dispersion liquid in a state of being uniformly dispersed in the pigment dispersant solution. The pigments may be dispersed individually or in combination.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamide, and acrylic pigment dispersants. These pigment dispersants may be used alone or in combination of 2 or more. Examples of the pigment dispersant include KP (manufactured by shin-Etsu chemical Co., Ltd.), FLOWLEN (manufactured by Kyoho chemical Co., Ltd.), Solsperse (manufactured by Zeneca), EFKA (manufactured by BASF Co., Ltd.), AJISPER (manufactured by AJISPER Fine chemical Co., Ltd.), Disperbyk (manufactured by BYK-Chemie Co., Ltd.) and the like.

When the pigment dispersant is used, the amount thereof is preferably 100 parts by mass or less, and more preferably 5 to 50 parts by mass, per 100 parts by mass of the pigment. When the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.

The colorant (a) preferably contains 1 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 adjustment of chromaticity.

The red pigment more preferably contains at least any one of c.i. pigment red 144, 177, 242, 254, 269 and 291 among the above-mentioned pigments, more preferably contains at least any one of an azo pigment, a diketopyrrolopyrrole pigment (having the same meaning as c.i. pigment red 291), an anthraquinone pigment, a xanthene pigment and a perylene pigment, and particularly preferably contains at least any one of c.i. pigment red 177 and 291. The red pigment may be used in combination with a yellow pigment, an orange pigment, or the like.

The green pigment more preferably contains at least any one of c.i. pigment green 58 and 59 among the above-described pigments. The green pigment may be used in combination with a yellow pigment.

The blue pigment more preferably contains at least any one of c.i. pigment blue 15, 15:3, 15:4, and 15:6 in the above-described pigments, and particularly preferably contains at least c.i. pigment blue 15: 6. The blue pigment may be used in combination with the violet pigment, or may be used in combination with a dye described later.

The yellow pigment more preferably contains at least any one of c.i. pigment yellow 129, 138, 139, 150, 185, and 231, more preferably at least any one of a quinophthalone pigment, a metal-containing pigment, and an isoindoline pigment, and particularly preferably at least c.i. pigment yellow 150, among the above-described pigments.

[ dye ]

Examples of The dye include known dyes, such as solvent dyes, acid dyes, direct dyes, and mordant dyes, and examples thereof include compounds classified into dyes such as solvent, acid, basic, reactive, direct, disperse, mordant, and vat dyes in The color index (published by The Society of Dyers and Colourists), and known dyes described in dyeing guidelines (chromo). The dye may be appropriately selected according to the desired spectral spectrum of the color filter. These dyes may be used alone, or 2 or more of them may be used in combination. The dye is preferably an organic solvent soluble dye.

Specific examples of the dye include c.i. solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189;

c.i. 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;

c.i. solvent orange 2, 7, 11, 15, 26, 56, 77, 86;

c.i. solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

c.i. solvent blue 4,5, 14, 18, 35, 36, 37, 45, 58, 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;

C.I. solvent dyes such as C.I. solvent green 1,3, 4,5, 7, 28, 29, 32, 33, 34 and 35,

C.i. acid yellow 1,3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

c.i. 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, 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;

c.i. acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

c.i. acid violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;

c.i. 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, 90:1, 91, 92, 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, 243, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 267, 256, 259, 280, 278, 296, 285, 315, 285, 340, 269;

c.i. acid green 1,3,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50: 1. 58, 63, 65, 80, 104, 105, 106, 109 and the like, and a pharmaceutically acceptable carrier,

C.i. 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;

c.i. 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;

c.i. direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

c.i. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

c.i. 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, 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, 244, 246, 247, 245, 250, 251, 252, 257, 275, 268, 293, 268, 248;

c.i. direct dyes such as c.i. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc,

C.i. disperse yellow 51, 54, 76;

c.i. disperse violet 26, 27;

C.I. disperse dyes such as C.I. disperse blues 1, 14, 56 and 60,

C.i. basic red 1, 10;

c.i. 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;

c.i. basic violet 2;

c.i. basic red 9;

C.I. basic dyes such as C.I. basic green 1,

C.i. reactive yellow 2, 76, 116;

c.i. reactive orange 16;

C.I. reactive dyes such as C.I. reactive red 36,

C.i. media yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

c.i. 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;

c.i. intermediate orange 3,4,5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

c.i. intermediate 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;

c.i. 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;

c.i. mediator dyes such as c.i. mediator green 1,3, 4,5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53, etc,

C.i. vat dyes such as c.i. vat green 1, and the like.

Further, examples of the dye include 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, tetraazaporphyrin dyes, and the like, depending on the chemical structure.

The dyes are preferably the following dyes (a1) to (a 4).

[ dye (A1) ], a process for producing the same, and a dye composition

The dye (A1) contains a salt represented by the formula (A-IV). The dye (a1) also includes tautomers thereof.

[ in the formula (A-IV), R^1A～R^8AEach 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 methylene groups constituting the saturated hydrocarbon group.

R^9A～R^12AEach 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 aryl group and the aralkyl group may have a substituent of-SO₃ ^-or-SO₂－N^-－SO₂－R^fAn oxygen atom may be inserted between methylene groups constituting the saturated hydrocarbon group, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom or an amino group which may have a substituent. R^9AAnd R^10AMay be bonded and form a ring together with the nitrogen atom to which they are bonded, R^11AAnd R^12AMay be bonded and form a ring together with the nitrogen atom to which they are bonded.

A represents an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms or an optionally substituted aromatic heterocyclic group having 3 to 20 carbon atoms, and the optionally substituted aromatic hydrocarbon group and the optionally substituted aromatic heterocyclic group may be-SO₃ ^-or-SO₂－N^-－SO₂－R^f。

[Y]^(m-n)-Represents an arbitrary (m-n) valent anion.

m represents an arbitrary natural number.

n represents-SO as a substituent₃ ^-or-SO₂－N^-－SO₂－R^fThe number of (3) is 0 or 1.

R^fRepresents a fluoroalkyl group having 1 to 12 carbon atoms.]

R^1A～R^12AThe saturated hydrocarbon group having 1 to 20 carbon atoms 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.

As R^1A～R^12AExamples of the group which is a saturated hydrocarbon group having 1 to 20 carbon atoms and in which an oxygen atom is inserted between methylene groups constituting the saturated hydrocarbon group include groups represented by the following formulae. In the following formula, a represents a bonding site to a carbon atom or a nitrogen atom.

Among these, a saturated hydrocarbon group having 1 to 10 carbon atoms is preferable, and an oxygen atom is inserted between methylene groups constituting the saturated hydrocarbon group, and a saturated hydrocarbon group having 1 to 6 carbon atoms is more preferable, and an oxygen atom is inserted between methylene groups constituting the saturated hydrocarbon group.

As R^9A～R^12AExamples of the aryl group having 6 to 20 carbon atoms in the above group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a phenylphenyl group.

As R^9A～R^12AExamples of the aralkyl group having 7 to 20 carbon atoms in (A) include benzyl, phenylethyl and methylphenylethyl.

As R^9A～R^12AExamples of the optionally substituted amino group in (1) include a methylamino group and an ethylamino groupAn amino group having an alkyl group having 1 to 4 carbon atoms, such as a primary amino group; an amino group having an alkyl group having 2 carbon atoms of 1 to 4, such as a dimethylamino group, a diethylamino group, or an ethylmethylamino group; amino groups, and the like.

As R^9A～R^12AExamples of the saturated hydrocarbon group having 1 to 20 carbon atoms and having a halogen atom or a substituted amino group in (1) include a trifluoromethyl group, a trifluoroethyl group, a chloroethyl group, a bromoethyl group, an iodoethyl group, an N, N-dimethylaminoethyl group, a pentafluoropropyl group, a chlorohexyl group, a bromohexyl group, an iodohexyl group, and an N, N-dimethylaminohexyl group.

R^9A～R^12AAs the substituent in the aryl group which may have a substituent and the aralkyl group which may have a substituent, other than the above-mentioned-SO₃ ^-or-SO₂－N^-－SO₂－R^fIn addition, halogen atoms such as fluorine atom, chlorine atom, iodine atom, etc.; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a sulfo group; a sulfamoyl group; and C1-6 alkylsulfonyl such as methylsulfonyl.

As R^fExamples of the fluoroalkyl group having 1 to 12 carbon atoms include a trifluoromethyl group and a2, 2, 2-trifluoroethyl group.

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 formula, a represents a bonding site to a nitrogen atom.

As R^9AAnd R^10AA ring bonded and formed together with the nitrogen atom to which they are bonded, and R^11AAnd R^12AExamples of the ring bonded to the nitrogen atom to which they are bonded include pyrrolidine ring, morpholine ring, and piperidine ringA ring, a piperazine ring, and the like.

From the viewpoint of ease of synthesis, R^1A～R^8APreferably, each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, and more preferably each independently represents a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom.

From the viewpoint of ease of synthesis, R^9A～R^12APreferably 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 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 by 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 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 by 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 or benzyl group include groups represented by the following formulae. In the following formula, a represents a bonding site to a nitrogen atom.

Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms in A include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, a phenanthryl group, a phenylphenyl group, and the like.

Examples of the aromatic hydrocarbon group which may have a substituent(s) represented by A include groups represented by the following formulae. Denotes the bonding site to a carbon atom.

The aromatic heterocyclic group represented by a means an aromatic group having at least 1 hetero atom as a constituent of a ring. Examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom and the like.

A is preferably an aromatic heterocyclic group having at least 1 nitrogen atom as a ring constituent. Examples of the aromatic heterocyclic group include five-membered aromatic heterocyclic groups having a nitrogen atom such as a pyrrolyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, and a triazolyl group; a six-membered aromatic heterocyclic group having a nitrogen atom such as a pyridyl group (pyridinyl), a pyridazinyl group and the like; a fused aromatic heterocyclic group such as a benzimidazolyl group and an indolyl group.

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, an amino group which may have a substituent, and the like, and specific examples thereof include the same as R^9A～R^12AThe same substituents as those exemplified in (1) above.

A is preferably a group represented by the formula (t 1).

[ in the formula (t1),

R⁵⁶represents 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.

X2 represents-O-, -N (R)⁵⁷) -or-S-.

R⁵⁷Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R⁴⁵And R⁴⁶Each 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 a substituentThe aralkyl group having 7 to 30 carbon atoms, wherein when the saturated hydrocarbon group has 2 to 20 carbon atoms, the saturated hydrocarbon group contains-CH₂-may be substituted with at least one of-O-and-CO-. wherein-CH adjacent to the C2-20 saturated hydrocarbon group₂-not simultaneously substituted by-O-, terminal-CH₂-is not substituted by-O-or-CO-. R⁴⁵And R⁴⁶May be bonded and form a ring together with the nitrogen atom to which they are bonded.

Denotes the bonding site to the carbenium ion. ]

Examples of the aromatic heterocyclic group which may have a substituent(s) and which represents A include groups represented by the following formulae. Denotes the bonding site to a carbon atom.

X2 is preferably-S-.

R⁵⁶Preferably an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably an optionally substituted phenyl group.

R⁴⁵And R⁴⁶The aromatic hydrocarbon group may be 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 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 an aromatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent on one side and 6 to 12 carbon atoms which may have a substituent on the other side.

A is preferably a group represented by the formula (A1-12) or the formula (A1-13).

As [ Y ]]^(m-n)Examples thereof include known anions, and from the viewpoint of heat resistance, preferred are boron-containing anions, aluminum-containing anions, fluorine-containing anions, and anions containing at least 1 element selected from tungsten, molybdenum, silicon, and phosphorus, and oxygen.

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

[ in the formula (4), W¹And W²Each independently represents a group having at least 2 monovalent proton donor substituents and having 2 substituents resulting from the release of protons from the group. M represents a boron atom or an aluminum atom.]

Examples of the group having at least 2 monovalent proton donor substituents and having 2 substituents which release protons from the group include groups in which at least 2 monovalent proton donor substituents (for example, a hydroxyl group, a carboxyl group, or the like) release protons from 2 proton donor substituents in a compound having at least 2 monovalent proton donor substituents. Preferred examples of the compound include catechol 2, 3-dihydroxynaphthalene, 2' -biphenol, 3-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-hydroxy-2-naphthoic acid, binaphthol, salicylic acid, benzilic acid, and mandelic acid, and these may have a substituent.

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; an amino group.

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

[ in the formula, R⁶¹、R⁶²、R⁶³And R⁶⁴Each 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.]

Examples thereof include anions (BC-1) to (BC-28) described below. M represents a boron atom or an aluminum atom. tBu in Table 1 represents a tert-butyl group.

[ Table 1]

Anion(s)	R61	R62	R63	R64
					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)	NH2	H	H	H
					Anion (BC-15)	H	NH2	H	H
Anion (BC-16)	H	H	NH2	H
					Anion (BC-17)	H	H	H	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

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

In [ formula (6), W³And W⁴Each independently represents a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms, or W³And W⁴Bonded to form a C1-4 fluoroalkanediyl group.]

[ in the formula (7), W⁵、W⁶And W⁷Each independently represents a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms.]

[ in the formula (8), Y¹Represents a C1-4 fluoroalkanediyl group.]

[ in the formula (9), Y²Represents a C1-4 fluoroalkyl group.]

As represented by W in formulae (6) and (7)³～W⁷Each represents a C1-4 fluoroalkyl group, preferably a perfluoroalkyl group, and examples thereof include-CF₃、－CF₂CF₃、－CF₂CF₂CF₃、－CF(CF₃)₂、－CF₂CF₂CF₂CF₃、－CF₂CF(CF₃)₂、－C(CF₃)₃And the like.

As W in formula (6)³And W⁴A C2-4 fluoroalkanediyl group, preferably a perfluoroalkanediyl group, bonded thereto, and examples thereof include-CF₂CF₂－、－CF₂CF₂CF₂－、－CF₂CF₂CF₂CF₂-and the like.

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

As Y in formula (9)²The fluoroalkyl group having 1 to 4 carbon atoms is preferably a perfluoroalkyl group, and may include-CF₃、－CF₂CF₃、－CF₂CF₂CF₃、－CF(CF₃)₂、－CF₂CF₂CF₂CF₃、－CF₂CF(CF₃)₂、－C(CF₃)₃And the like.

Examples of the anion represented by the formula (6) (hereinafter, may be referred to as "anion (6)") include the following anions (6-1) to (6-6).

Examples of the anion represented by formula (7) (hereinafter, may be referred to as "anion (7)") include the following anion (7-1).

Examples of the anion represented by the formula (8) (hereinafter, may be referred to as "anion (8)") include the following anions (8-1) to (8-4).

Examples of the anion represented by formula (9) (hereinafter, may be referred to as "anion (9)") include the following anions (9-1) to (9-4).

[Y]^(m-n)-Preferably an anion containing at least 1 element selected from tungsten, molybdenum, silicon and phosphorus, and oxygen. As [ Y ] containing tungsten]^(m-n)-Anions of heteropolyacids or isopoly acids are preferred, and anions of phosphotungstic acid, silicotungstic acid and tungsten isopoly acids are more preferred.

Examples of anions of such heteropoly-or isopoly-acids containing tungsten include Keggin-type phosphotungstic acid ion alpha- [ PW₁₂O₄₀]^3-Dawson type phosphotungstic acid ion alpha- [ P [ ]₂W₁₈O₆₂]^6-、β－[P₂W₁₈O₆₂]^6-Keggin type silicotungstic acid ion alpha- [ SiW₁₂O₄₀]^4-、β－[SiW₁₂O₄₀]^4-、γ－[SiW₁₂O₄₀]^4-And as other examples [ P₂W₁₇O₆₁]^10-、[P₂W₁₅O₅₆]^12-、[H₂P₂W₁₂O₄₈]^12-、[NaP₅W₃₀O₁₁₀]^14-、α－[SiW₉O₃₄]^10-、γ－[SiW₁₀O₃₆]^8-、α－[SiW₁₁O₃₉]^8-、β－[SiW₁₁O₃₉]^8-、[W₆O₁₉]^2-、[W₁₀O₃₂]^4-、WO₄ ^2-And the like.

Examples of the anion composed of at least 1 element selected from silicon and phosphorus and oxygen include SiO₃ ^2-、PO₄ ^3-。

Particularly, heteropoly acid anions such as Keggin-type phosphotungstic acid ion, Dawson-type phosphotungstic acid ion and Keggin-type silicotungstic acid ion, [ W ] are preferable from the viewpoint of ease of synthesis and post-treatment₁₀O₃₂]^4-An equivalent polyacid anion.

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

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

Having a sulfo group (-SO)₃H) When the substituent is a hydrogen cation, the hydrogen cation may be exchanged with an arbitrary cation to form a salt. As an arbitrary cation, there may be mentioned,examples thereof include alkali metal ions, organic ammonium ions, and optionally substituted imidazolium ions. When a plurality of sulfo groups are present, a salt may be formed with a divalent or more metal ion.

[ dye (A2) ], a process for producing the same, and a dye composition

The dye (a2) comprises a xanthene dye. As the xanthene dye, known ones can be used. Hereinafter, the dye (a2) is also referred to as a xanthene dye (a 2).

The xanthene dye (a2) is a dye containing a compound having a xanthene skeleton in the molecule. Examples of the xanthene dye (a2) include c.i. acid red 51 (hereinafter, the description of c.i. acid red is omitted, and only the number is described, the same applies to the others), 52, 87, 92, 94, 289, 388, c.i. acid violet 9, 30, 102, c.i. basic red 1 (rhodamine 6G), 2,3,4, 8, c.i. basic red 10, 11, c.i. basic violet 10 (rhodamine B), 11, c.i. solvent red 218, c.i. intermediate red 27, c.i. active red 36 (mangifer B), sulforhodamine G, the xanthene dye described in japanese patent application laid-open No. 2010-32999, and the xanthene dye described in patent No. 4492760. Xanthene dyes dissolved in organic solvents are preferred.

Among them, the xanthene dye (a2) is preferably a dye containing a compound represented by the formula (1a) (hereinafter, may be referred to as "compound (1 a)"). The compound (1a) may also be a tautomer thereof. When the compound (1a) is used, the content of the compound (1a) in the xanthene dye (a2) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. In particular, as the xanthene dye (a2), it is preferable to use only the compound (1 a).

[ in the formula (1a), R^1a～R^4aEach 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-CH is contained in the saturated hydrocarbon group₂May be substituted by-O-, -CO-or-NR^11a-substitution. R^1aAnd R^2aMay together form a ring containing a nitrogen atom, R^3aAnd R^4aMay together form a ring containing a nitrogen atom.

R^5arepresents-OH or-SO₃ ^-、－SO₃H、－SO₃ ^-Za⁺、－CO₂H、－CO₂ ^-Za⁺、－CO₂R^8a、－SO₃R^8aor-SO₂NR^9aR^10a。

R^6aAnd R^7aEach independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

m represents an integer of 0 to 5. When m is 2 or more, plural R^5aMay be the same or different.

a represents an integer of 0 or 1.

Xa represents a halogen atom.

Za⁺To represent⁺N(R^11a)₄、Na⁺Or K⁺4 of R^11aMay be the same or different.

R^8aRepresents 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.

R^9aAnd R^10aEach independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent, the saturated hydrocarbon group containing-CH₂May be substituted by-O-, -CO-, -NH-or-NR^8a-substituted, R^9aAnd R^10aCan be bonded to each other to form a three-to ten-membered nitrogen-containing member ring.

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

In the formula (1a), SO is present₃ ^-In this case, the number of the cells is 1.

As R^1a～R^4aIn the above (C6-10) monovalent aromatic hydrocarbon group, for example, phenyl group, tolyl group, xylyl group, mesityl group, propylphenyl group and butyl groupPhenyl, and the like.

Examples of the substituent which may be contained in the aromatic hydrocarbon group include a halogen atom, a carboxyl group and-R^8a、－OH、－OR^8a、－SO₃ ^-、－SO₃H、－SO₃ ^-Za⁺、－CO₂H、－CO₂R^8a、－SR^8a、－SO₂R^8a、－SO₃R^8aor-SO₂NR^9aR^10a。

Among them, as the substituent, preferred is-SO₃ ^-、－SO₃H、－SO₃ ^-Za⁺and-SO₂NR^9aR^10aMore preferably-SO₃ ^-Za⁺and-SO₂NR^9aR^10a. as-SO at this time₃ ^-Za⁺preferably-SO₃ ^-+N(R^11a)₄。

As R^1a～R^4aAnd R^8a～R^11aThe monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in (b) includes, for example, a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a hexadecyl group, or an eicosyl group; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl groups; and (c) 3-20 alicyclic saturated hydrocarbon groups such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl.

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

R^9aAnd R^10aThe hydrogen atom contained in the saturated hydrocarbon group in (1) may be substituted with a hydroxyl group or a halogen atom, for example.

As R^1aAnd R^2aTogether form a ring, and R^3aAnd R^4aExamples of the ring to be formed together include the following rings.

as-OR^8aExamples thereof include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, and eicosyloxy group.

as-CO₂R^8aExamples thereof include methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl, and eicosyloxycarbonyl.

As a-SR^8aExamples thereof include methylthio, ethylthio, butylthio, hexylthio, decylthio and eicosylthio.

as-SO₂R^8aExamples thereof include methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, decylsulfonyl group and eicosylsulfonyl group.

as-SO₃R^8aExamples thereof include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexyloxysulfonyl, and eicosyloxysulfonyl.

as-SO₂NR^9aR^10aFor example, a sulfamoyl group;

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- (3-methylbutyl) sulfamoyl, N-cyclopentylsulfamoyl, N-hexylsulfamoyl, N- (1, 3-dimethylbutyl) sulfamoyl, N- (3, 3-dimethylbutyl) sulfamoyl, N-heptylsulfamoyl, N-1 substituted sulfamoyl groups such as 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;

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

R^5apreferably-CO₂H、－CO₂ ^-Za⁺、－CO₂R^8a、－SO₃ ^-、－SO₃ ^-Za⁺、－SO₃H or-SO₂NHR^9aMore preferably-SO₃ ^-、－SO₃ ^-Za⁺、－SO₃H or-SO₂NHR^9a。

m is preferably 1 to 4, more preferably 1 or 2.

As R^6aAnd R^7aThe alkyl group having 1 to 6 carbon atoms in (A) includes the alkyl groups having 1 to 6 carbon atoms in the above-mentioned alkyl groups.

As R^11aExamples of the aralkyl group having 7 to 10 carbon atoms in (A) include benzyl, phenylethyl, phenylbutyl and the like.

Za⁺Is composed of⁺N(R^11a)₄、Na⁺Or K⁺Preferably, it is⁺N(R^11a)₄。

As mentioned above⁺N(R^11a)₄Preferably 4R^11aAt least 2 of them are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. In addition, 4R^11aThe total number of carbon atoms of (1) is preferably 20 to 80, more preferably 20 to 60.

The compound (1a) is preferably a compound represented by the formula (2a) (hereinafter, may be referred to as "compound (2 a)"). The compound (2a) may also be a tautomer thereof.

[ in the formula (2a), R^21a～R^24aEach independently represents a hydrogen atom, -R^26aOr a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. R^21aAnd R^22aMay together form a ring containing a nitrogen atom, R^23aAnd R^24aMay together form a ring containing a nitrogen atom.

R^25arepresents-SO₃ ^-、－SO₃H、－SO₃ ^-Z1⁺or-SO₂NHR^26a。

m1 represents an integer of 0 to 5. When m1 is 2 or more, plural R' s^25aMay be the same or different.

a1 represents an integer of 0 or 1.

X1 represents a halogen atom.

R^26aRepresents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms and optionally having a halogen atom or a carboxyl group.

Z1⁺To represent⁺N(R^27a)₄、Na⁺Or K⁺4 of R^27aMay be the same or different.

R^27aRepresents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group.]

As R^21a～R^24aIn the above formula, the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms includes the group represented by R^1a～R^4aThe same applies to the aromatic hydrocarbon group as mentioned above. The hydrogen atom contained in the aromatic hydrocarbon group may be replaced by-SO₃ ^-、－SO₃H、－SO₃ ^-Z1⁺、－SO₃R^26aor-SO₂NHR^26aAnd (4) substitution.

As R^21a～R^24aIn a combination of (1), preferably R^21aAnd R^23aIndependently of each other, a hydrogen atom or a saturated hydrocarbon having 1 to 10 carbon atomsA group (the saturated hydrocarbon group may have a halogen atom or a carboxyl group), R^22aAnd R^24aIs a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms and hydrogen atoms contained in the aromatic hydrocarbon group are replaced by-SO₃ ^-、－SO₃H、－SO₃ ^-Z1⁺、－SO₃R^26aor-SO₂NHR^26aCombinations of substitutions. A further preferred combination is R^21aAnd R^23aIndependently represents 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^22aAnd R^24aIs a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms and hydrogen atoms contained in the aromatic hydrocarbon group are replaced by-SO₃ ^-Z1⁺or-SO₂NHR^26aCombinations of substitutions.

As R^21aAnd R^22aTogether form a ring containing a nitrogen atom, and R^23aAnd R^24aExamples of the ring containing a nitrogen atom formed together with R^1aAnd R^2aThe rings formed together are identical rings. Among them, aliphatic heterocyclic rings are preferable. Examples of the aliphatic heterocyclic ring include the following.

As R^26aAnd R^27aIn the above (A), the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms is represented by^8a～R^11aThe same groups as those mentioned for the saturated hydrocarbon group in (1).

R^21a～R^24ais-R^26aWhen is, -R^26aPreferably each independently is methyl or ethyl. In addition, as-SO₃R^26aand-SO₂NHR^26aR in (1)^26aA branched alkyl group having 3 to 20 carbon atoms is preferable, a branched alkyl group having 6 to 12 carbon atoms is more preferable, and a 2-ethylhexyl group is further preferable.

Z1⁺Is composed of⁺N(R^27a)₄、Na⁺Or K⁺Preferably, it is⁺N(R^27a)₄。

As mentioned above⁺N(R^27a)₄Preferably 4R^27aAt least 2 of them are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. In addition, 4R^27aThe total number of carbon atoms of (1) is preferably 20 to 80, more preferably 20 to 60.

m1 is preferably 1 to 4, more preferably 1 or 2.

Further, as the compound (1a), a compound represented by the formula (3a) (hereinafter, may be referred to as "compound (3 a)") is also preferable. The compound (3a) may also be a tautomer thereof.

[ in the formula (3a), R^31aAnd R^32aEach independently represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms, a carboxyl group or a halogen atom, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms, or-CH contained in the saturated hydrocarbon group₂May be substituted by-O-, -CO-or-NR^11a-substitution.

R^33aAnd R^34aEach 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.

R^31aAnd R^33aMay together form a ring containing a nitrogen atom, R^32aAnd R^34aMay together form a ring containing a nitrogen atom.

p and q each independently represent an integer of 0 to 5. When p is 2 or more, plural R^33aMay be the same or different, and when q is 2 or more, plural R' s^34aMay be the same or different.

R^11aThe same meanings as described above are indicated.]

As R^31aAnd R^32aIn the (C1-C10) monovalent saturated hydrocarbon group, R is^8aOne of (1) toA group having 1-10 carbon atoms in a saturated hydrocarbon group.

The aromatic hydrocarbon group having 6 to 10 carbon atoms which may be a substituent may be mentioned^1aThe aromatic hydrocarbon group in (1) is the same as that in (2).

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

R^31aAnd R^32aThe monovalent saturated hydrocarbon groups are preferably, independently of each other, a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms (the saturated hydrocarbon group may have a halogen atom or a carboxyl group).

As R^33aAnd R^34aExamples of the alkyl group having 1 to 4 carbon atoms in (A) include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a secondary propyl group, and a tertiary butyl group.

As R^33aAnd R^34aExamples of the alkylthio group having 1 to 4 carbon atoms in the group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, and an isopropylthio group.

As R^33aAnd R^34aExamples of the alkylsulfonyl group having 1 to 4 carbon atoms in (A) include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group and isopropylsulfonyl group.

R^33aAnd R^34aThe alkyl group having 1 to 4 carbon atoms is preferable, and the methyl group is more preferable.

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

Examples of the compound (1a) include compounds represented by the formulae (1-1) to (1-107). In the formula, R^40aRepresents 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. R^26aHaving the formula (2a) with R^26aThe same meaning is used.

Among the above compounds, the compounds represented by the formulae (1-1) to (1-23), the formulae (1-37) to (1-85), and the formulae (1-102) to (1-107) correspond to the compound (2a), and the compounds represented by the formulae (1-24) to (1-36), and the formulae (1-86) to (1-101) correspond to the compound (3 a).

Among them, a sulfonamide of c.i. acid red 289, a quaternary ammonium salt of c.i. acid red 289, a sulfonamide of c.i. acid violet 102, or a quaternary ammonium salt of c.i. acid violet 102 is preferable. Examples of such compounds include compounds represented by formulae (1-1) to (1-8), formulae (1-11), and formulae (1-12).

Further, compounds represented by the formulae (1-24) to (1-33) are also preferable from the viewpoint of excellent solubility in organic solvents.

From the viewpoint of satisfactory chromaticity region and transmittance of the obtained coating film, compounds represented by the formulae (1-32), (1-44) and (1-97) are also preferable.

As the xanthene dye (A2), a commercially available xanthene dye (for example, "Chugai amino Fast Pink R-H/C" manufactured by Zhongzhou Kabushiki Kaisha, and "Rhodamin 6G" manufactured by Tiangang chemical industry) can be used. Alternatively, a commercially available xanthene dye may be synthesized as a starting material with reference to Japanese patent application laid-open No. 2010-32999.

[ dye (A3) ], a process for producing the same, and a dye composition

The dye (a3) comprises an anthraquinone dye. As the anthraquinone dye, a known one can be used. Examples of the anthraquinone dye include:

c.i. solvent yellow 117 (hereinafter, the description of c.i. solvent yellow is omitted, and only the number is written), 163, 167, 189,

C.I. solvent orange 77, 86,

C.i. solvent red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247,

c.i. solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60, c.i. solvent violet,

C.i. solvent blue 14, 18, 35, 36, 45, 58, 59: 1. 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139, 9,

C.I. solvent Green 3, 28, 29, 32, 33,

C.I. acid red 80,

C.I. acid Green 25, 27, 28, 41,

C.I. acid violet 34,

C.i. acid blue 25, 27, 40, 45, 78, 80, 112,

C.I. disperse yellow 51,

C.I. disperse Violet 26, 27,

C.I. disperse blues 1, 14, 56, 60,

C.I. direct blue 40,

C.I. media Red 3, 11,

C.i. mordant blue 8, and the like.

The anthraquinone dye is preferably dissolved in an organic solvent.

[ dye (A4) ], a process for producing the same, and a dye composition

The dye (a4) comprises a porphyrazine dye. The porphyrazine dye is a compound having a porphyrazine skeleton in a molecule. When the porphyrazine dye is an acid dye or a basic dye, the dye may form a salt with any cation or anion.

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 still more preferably 5 to 50% by mass, based on the total amount of solid components 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.

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

The colorant (a) preferably contains the above-mentioned pigment and at least 1 selected from the dyes (a1) to (a 4).

When the colorant (a) contains the dye (a1), the colorant (a) may be contained in the form of a dispersion liquid in which the dye (a1) is dispersed in a solvent.

In another embodiment, the colorant (a) preferably contains a pigment and a xanthene dye (a2), more preferably contains a pigment and a compound represented by the formula (1a), further preferably contains a pigment and a compound represented by the formula (2a), particularly preferably contains a pigment and a compound represented by the formula (3a), and more particularly preferably contains a pigment and at least 1 selected from the group consisting of a compound represented by the formula (1-32), a compound represented by the formula (1-44), and a compound represented by the formula (1-97).

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 still more preferably 81 to 99% by mass.

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 still more preferably 0.5 to 20% by mass.

When the colorant (a) contains the dyes (a1) and (a2), the mass ratio [ (a1): (a2) ] of the dye (a1) to the dye (a2) in the colorant (a) 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.

When the colorant (a) contains the dye (a2) and the pigment, the mass ratio [ (a2): pigment ] of the dye (a2) to the pigment in the colorant (a) may be, for example, 1:99 to 99:1, preferably 5:95 to 50:50, and more preferably 10:90 to 30: 70.

When the colored curable resin composition contains a solvent (hereinafter, also referred to as solvent (E)), a colorant-containing liquid containing the colorant (a) and the solvent (E) may be prepared in advance, and then the colorant-containing liquid may be used to prepare the colored curable resin composition. When the colorant (a) is insoluble in the solvent (E), a liquid containing the colorant can be prepared as a dispersion by dispersing the colorant (a) and mixing the dispersion with the solvent (E). The colorant-containing liquid may contain a part or all of the solvent (E) contained in the colored curable resin composition.

The content of the solid content in the colorant-containing liquid is preferably 0.1 to 99.9% by mass, more preferably 1 to 90% by mass, even more preferably 1 to 60% by mass, and particularly preferably 3 to 50% by mass, based on the total amount of the colorant-containing liquid.

The content of the colorant (a) in the colorant-containing liquid is preferably 0.01 to 100% by mass, more preferably 0.1 to 99.9% by mass, even more preferably 1 to 99% by mass, and particularly preferably 10 to 90% by mass, of the total amount of solid components in the colorant-containing liquid.

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

The colorant (a) can be dispersed by a dispersing agent to obtain a state in which the colorant (a) is uniformly dispersed in a liquid containing the colorant.

The dispersant may be any of cationic, anionic, nonionic and amphoteric surfactants. Specifically, there may be mentioned polyester, polyamide, acrylic and other surfactants. These dispersants may be used alone or in combination of two or more. Examples of the dispersant include KP (manufactured by shin-Etsu chemical Co., Ltd.), FLOWLEN (manufactured by Kyoho chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca), EFKA (registered trademark) (manufactured by BASF (manufactured by Co., Ltd.), AJISPER (registered trademark) (manufactured by AJIOBYR Fine chemical Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), BYK (registered trademark) (manufactured by BYK-Chemie (manufactured by Co., Ltd.), and the like.

In order to prepare the colorant-containing liquid, when a dispersant is used, the amount of the dispersant (solid content) to be used is preferably 5 to 100 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the colorant (a). When the amount of the dispersant used is within the above range, a more uniformly dispersed liquid containing a colorant tends to be obtained.

[2] resin (B)

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

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

Resin [ K1 ]: a copolymer having a structural unit derived from at least 1 [ hereinafter, sometimes referred to as "monomer (a)") selected from unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and a structural unit derived from a monomer [ hereinafter, sometimes referred to as "monomer (b)" ] having a cyclic ether structure of 2 to 4 carbon atoms and an ethylenically unsaturated bond.

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

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

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

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).

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

The resins [ K1] to [ K6] may be copolymers or resins described below.

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

Resin [ K2 ]: a copolymer of monomer (a) with monomer (b) and monomer (c).

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

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

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

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

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

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

In the present specification, "(meth) acrylic acid" means at least 1 selected from acrylic acid and methacrylic acid. The same applies to "(meth) acryloyl group" and "(meth) acrylate" and the like.

The monomer (b) is a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least 1 selected from an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (an oxetane ring)) and an ethylenically unsaturated bond. The monomer (b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

Examples of the monomer (b) include a monomer having an oxetanyl group and an ethylenically unsaturated bond [ hereinafter, sometimes referred to as "monomer (b 1)" ], a monomer having an oxetanyl group and an ethylenically unsaturated bond [ hereinafter, sometimes referred to as "monomer (b 2)" ], a monomer having a tetrahydrofuranyl group and an ethylenically unsaturated bond [ hereinafter, sometimes referred to as "monomer (b 3)" ], and the like.

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

Examples of the monomer (b 1-1) include glycidyl (meth) acrylate, β -methylglycidyl (meth) acrylate, β -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α -methyl-o-vinylbenzyl glycidyl ether, α -methyl-m-vinylbenzyl glycidyl ether, α -methyl-p-vinylbenzyl glycidyl ether, 2, 3-bis (glycidoxymethyl) styrene, 2, 4-bis (glycidoxymethyl) styrene, 2, 5-bis (glycidoxymethyl) styrene, 2, 6-bis (glycidoxymethyl) styrene, 2,3, 4-tris (glycidoxymethyl) styrene, 2,3, 5-tris (glycidoxymethyl) styrene, 2,3, 6-tris (glycidoxymethyl) styrene, 3,4, 5-tris (glycidoxymethyl) styrene, 2,4, 6-tris (glycidoxymethyl) styrene and the like.

Examples of the monomer (b 1-2) include vinylcyclohexene monooxide, 1, 2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel chemical Co., Ltd.), (3, 4-epoxycyclohexylmethyl (meth) acrylate (e.g., Cyclomer A400; manufactured by Daicel chemical Co., Ltd.), (3, 4-epoxycyclohexylmethyl (meth) acrylate (e.g., Cyclomer M100; manufactured by Daicel chemical Co., Ltd.), (I) and (II).

In the formulae (I) and (II), R^aaAnd R^abIndependently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. X^a1And X^a2Independently of one another, represents a single bond, -R^ac－、*－R^ac－O－、*－R^ac-S-, or-R^ac－NH－。R^acRepresents an alkanediyl group having 1 to 6 carbon atoms. Denotes the bonding site to O.

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

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

R^aaAnd R^abPreferred 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.

As a constituent R^acExamples of the alkanediyl group include a methylene group, an ethylene group, a propane-1, 2-diyl group and a propane1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, etc.

X^a1And X^a2Preferably a single bond, methylene, ethylene, — CH₂-O- ('represents a bonding site to O)' -CH₂CH₂-O-radical, more preferably single bond, -CH₂CH₂-O-group.

Specific examples of the compounds represented by formula (I) include compounds represented by formulae (I-1) to (I-15), compounds represented by formulae (I-1), (I-3), formula (I-5), formula (I-7), formula (I-9), and formulae (I-11) to (I-15) are preferable, and compounds represented by formulae (I-1), formula (I-7), formula (I-9), and formula (I-15) are more preferable.

Specific examples of the compounds represented by the formula (II) include the compounds represented by the formulae (II-1) to (II-15), the compounds represented by the formulae (II-1), (II-3), (II-5), (II-7), (II-9), and the formulae (II-11) to (II-15) are preferable, and the compounds represented by the formulae (II-1), (II-7), (II-9), and (II-15) are more preferable.

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone, respectively. They may be mixed in any ratio. In the mixing, the mixing ratio is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and still more preferably 20:80 to 80:20 in terms of the molar ratio of formula (I) to formula (II).

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

Preferable examples of the monomer (b2) include 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, 3-methyl-3- (meth) acryloyloxyethyloxyoxetane and 3-ethyl-3- (meth) acryloyloxyethyloxyethyloxetane.

The monomer (b3) is preferably a monomer having a tetrahydrofuranyl group and a (meth) acryloyloxy group. Preferable examples of the monomer (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V #150, manufactured by Osaka chemical industries, Ltd.), tetrahydrofurfuryl methacrylate, and the like.

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, and tricyclo [5.2.1.0 ] meth) acrylate^2,6]Decan-8-yl ester (which is known as "dicyclopentyl (meth) acrylate" as a common name in the art, and may be referred to as "tricyclodecyl (meth) acrylate" in some cases), and tricyclo (meth) acrylate [5.2.1.0^2,6](meth) acrylates such as decen-8-yl ester (which is conventionally referred to in the art as "dicyclopentenyl (meth) acrylate"), (meth) acrylic acid esters such as dicyclopentenyl ethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, and benzyl (meth) acrylate;

hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

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

bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2 '-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5, 6-dihydroxybicyclo [2.2.1] hept-2-ene, 5, 6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-bis (2' -hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-dimethoxybicyclo [ 2.1] hept-2-ene, 5, 6-bis (2.1) hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxyhept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-2.1 ] hept-2-ene, 5-hydroxy-2-hydroxy-2-hydroxy-1-2-hydroxy-2-1-hydroxy-2-hydroxy-2-1-2-ethyl-2-ene, 5-hydroxy-2-hydroxy-2, 5, 6-2-hydroxy-2-one, 5-2-one, 5, 6-one, 2-one, 2-one, 5, Bicyclic unsaturated compounds such as 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonybicyclo [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;

dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate and N- (9-acridinyl) maleimide;

styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluenes, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene and the like.

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

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

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

structural units derived from monomer (b), in particular structural units derived from monomer (b 1): preferably 50 to 98 mol% (more preferably 55 to 90 mol%).

When the ratio of the structural unit of the resin [ K1] is in the above range, the storage stability, the developability, and the solvent resistance of the obtained pattern tend to be excellent.

The resin [ K1] can be produced by a method described in "Experimental method for Polymer Synthesis" (published by Otsuka institute of Engineers, 1 st edition, chemical Co., Ltd., 1972, 3 months and 1 days), and a cited reference described in the above document.

Specifically, the following methods are mentioned: the reaction vessel is charged with a predetermined amount of the monomer (a) and the monomer (b) (particularly the monomer (b1)), a polymerization initiator, a solvent, and the like, and the mixture is stirred, heated, and kept warm in a deoxygenated atmosphere. The polymerization initiator and the solvent used herein are not particularly limited, and polymerization initiators and solvents generally used in this field can be used. Examples of the polymerization initiator include azo compounds (e.g., 2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), and organic peroxides (e.g., benzoyl peroxide). The solvent may be any solvent that dissolves the monomers, and the solvent (E) described below as a solvent for the colored curable resin composition may be used.

The copolymer obtained may be used as it is as a solution after the reaction, may be used as a concentrated or diluted solution, or may be used as a substance taken out as a solid (powder) by a method such as reprecipitation. In particular, by using the solvent (E) described later as a solvent in the polymerization, the solution after the reaction can be used as it is, and the production process can be simplified.

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

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

structural units derived from monomer (b), in particular structural units derived from monomer (b 1): preferably 2 to 95 mol% (more preferably 5 to 80 mol%),

structural units derived from monomer (c): preferably 1 to 65 mol% (more preferably 5 to 60 mol%).

When the ratio of the structural unit of the resin [ K2] is in the above range, the storage stability, the developability, the solvent resistance of the obtained pattern, the heat resistance and the mechanical strength tend to be excellent.

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

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

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

structural units derived from monomer (c): preferably 45 to 98 mol% (more preferably 50 to 90 mol%).

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

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

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

structural units derived from monomer (c): preferably 50 to 95 mol% (more preferably 55 to 90 mol%).

Then, a cyclic ether structure having 2 to 4 carbon atoms of the monomer (b), particularly an oxirane ring of the monomer (b1), is reacted with a part of the carboxylic acid and/or carboxylic acid anhydride derived from the monomer (a) in the copolymer. Specifically, after a copolymer of the monomer (a) and the monomer (c) is produced, the atmosphere in the flask is then replaced with air from nitrogen, and the monomer (b) (particularly the monomer (b1)), a reaction catalyst for a carboxylic acid or a carboxylic anhydride and a cyclic ether structure (for example, tris (dimethylaminomethyl) phenol, etc.), a polymerization inhibitor (for example, hydroquinone, etc.), etc. are placed in the flask and reacted at 60 to 130 ℃ for 1 to 10 hours, whereby a resin [ K4] can be obtained.

The amount of the monomer (b), particularly the amount of the monomer (b1), used is preferably 5 to 80 mol, more preferably 10 to 75 mol, based on 100 mol of the monomer (a). When the content is within this range, the balance among storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity tends to be good. The monomer (b) used for the resin [ K4] is preferably the monomer (b1), and more preferably the monomer (b 1-1), because the cyclic ether structure has high reactivity and the unreacted monomer (b) is not likely to remain.

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

The reaction conditions such as the charging method, the reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like. Similarly to the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production facility, the amount of heat generated by polymerization, and the like.

As the first stage of the resin [ K5], a copolymer of the monomer (b) (particularly, the monomer (b1)) and the monomer (c) is obtained in the same manner as in the above-described method for producing the resin [ K1 ]. As described above, the copolymer obtained may be used as it is as a solution after the reaction, may be used as a concentrated or diluted solution, or may be used as a substance taken out as a solid (powder) by a method such as reprecipitation.

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

A structural unit derived from the monomer (b), particularly a structural unit derived from the monomer (b 1): preferably 5 to 95 mol% (more preferably 10 to 90 mol%),

structural units derived from monomer (c): preferably 5 to 95 mol% (more preferably 10 to 90 mol%).

Further, the resin [ K5] can be obtained by reacting the carboxylic acid or carboxylic anhydride contained in the monomer (a) with the cyclic ether structure derived from the monomer (b) contained in the copolymer of the monomer (b) (particularly, the monomer (b1)) and the monomer (c) under the same conditions as the production method of the resin [ K4 ]. The amount of the monomer (a) to be reacted with the copolymer is preferably 5 to 80 mol based on 100 mol of the monomer (b) (particularly, the monomer (b 1)). The monomer (b) used for the resin [ K5] is preferably the monomer (b1), and more preferably the monomer (b 1-1), because the cyclic ether structure has high reactivity and the unreacted monomer (b) is not likely to remain.

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

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).

Among the resins [ K1] to [ K6], the resin [ K1] or [ K2] is preferable as the resin (B). The resin (B) may be composed of 1 resin, or may contain 2 or more resins.

The weight average molecular weight (Mw) of the resin (B) in terms of polystyrene is preferably 3000 to 100000, more preferably 5000 to 50000, and still more preferably 5000 to 30000. When the weight average molecular weight (Mw) is in the above range, the unexposed portion tends to have high solubility in a developer, and the residual film ratio 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, more preferably 1.2 to 4.

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

The content of the resin (B) is preferably 1 to 65% by mass, more preferably 3 to 60% by mass, and still more 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 the resolution and the residual film ratio of the colored pattern tend to be improved.

In the case where a liquid containing a colorant is prepared in advance and then the liquid containing a colorant is used to prepare a colored curable resin composition, the liquid containing a colorant may contain a part or all, preferably a part, of the resin (B) described later contained in the colored curable resin composition in advance. The dispersion stability of the colorant-containing liquid can be further improved by previously containing the resin (B). It is preferable that the liquid containing the colorant contains the resin (B2) in advance.

The content of the resin (B) in the colorant-containing liquid may be, for example, 10000 parts by mass or less, preferably 5000 parts by mass or less, more preferably 1000 parts by mass or less, still more preferably 1 to 500 parts by mass, particularly preferably 5 to 200 parts by mass, and particularly preferably 10 to 100 parts by mass, per 100 parts by mass of the colorant (a).

[3] polymerizable Compound (C)

The polymerizable compound (C) is not particularly limited as long as it can be polymerized by an active radical or the like generated from the polymerization initiator (D) by light irradiation or the like, and examples thereof include a compound having a polymerizable ethylenically unsaturated bond (preferably, a (meth) acrylate compound). The weight average molecular weight of the polymerizable compound (C) is preferably 3000 or less, more preferably 1500 or less. The lower limit of the weight average molecular weight of the polymerizable compound (C) may be 50 or more, or may be 150 or more.

Among these, the polymerizable compound (C) is preferably a photopolymerizable compound having 3 or more ethylenically unsaturated bonds, and examples thereof include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, and mixtures thereof, Propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like. Among them, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like are preferable.

The colored curable resin composition of the present invention may contain 1 or 2 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, based on 100 parts by mass of the resin (B) in the colored curable resin composition.

The content of the polymerizable compound (C) is preferably 1 to 65% by mass, more preferably 3 to 60% by mass, and still more preferably 5 to 55% by mass, based on the total amount of the solid content. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming a colored pattern and the chemical resistance of the color filter tend to be improved.

[4] polymerization initiator (D)

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid, or the like under the action of light or heat to initiate polymerization, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include oxime compounds such as O-acyloxime compounds, alkylphenone compounds, bisimidazole compounds, triazine compounds, and acylphosphine oxide compounds.

In view of sensitivity, formability of a precise pattern shape, and the like, 2 or more polymerization initiators (D) may be used in combination. The polymerization initiator (D) preferably contains an oxime compound such as an O-acyloxime compound because it is advantageous in terms of sensitivity and precision in producing a pattern shape having a desired line width.

The O-acyloxime compound is a compound having a structure represented by formula (d). Hereinafter, the bonding site is denoted.

Examples of such O-acyloxime compounds include N-benzoyloxy-1- (4-phenylthiophenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylthiophenyl) octan-1-one-2-imine, N-benzoyloxy-1- (4-phenylthiophenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- { 2-methyl-4- (3, 3-dimethyl-2, 4-dioxopentylmethoxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-one-2-imine and the like, wherein the O-acyloxime compound is preferably at least 1 selected from the group consisting 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, OXE03 (both of which are available from BASF corporation) and N-1919 (available from ADEKA corporation) may also be used. When these O-acyloxime compounds are used, a color filter having excellent lithographic performance tends to be obtained.

The alkylphenone compound has a structure represented by the formula (d4) or a structure represented by the formula (d 5). Denotes the bonding site. In these structures, the benzene ring may have a substituent.

Examples of the compound having a structure represented by formula (d4) include 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, and 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [ 4- (4-morpholino) phenyl ] butan-1-one. Commercially available products such as Irgacure 369, 907, and 379 (all of which are manufactured by BASF corporation) may be used.

Examples of the compound having the structure represented by formula (d5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [ 4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone, benzildimethylketal, and the like.

In terms of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by the formula (d 4).

Examples of the biimidazole compound include 2,2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenylbiimidazole, 2' -bis (2, 3-dichlorophenyl) -4, 4 ', 5, 5' -tetraphenylbiimidazole (see, for example, japanese unexamined patent publication No. 6-75372, japanese unexamined patent publication No. 6-75373, etc.), 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenylimidazole, 2' -bis (2-chlorophenyl) -4, 4 ', 5, 5' -tetrakis (alkoxyphenyl) biimidazole, 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetrakis (dialkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4, 4 ', 5, 5' -tetrakis (trialkoxyphenyl) biimidazole (see, for example, japanese unexamined patent publication No. 48-38403, Japanese patent application laid-open No. 62-174204, etc.), bisimidazole compounds in which the phenyl group at the 4,4 ', 5, 5' -position is substituted with a carboalkoxy group (see, for example, Japanese patent application laid-open No. 7-10913, etc.), and the like. Among them, compounds represented by the following formula or mixtures thereof are preferable.

Examples of the triazine compound include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1, 3, 5-triazine, 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.

Examples of the acylphosphine oxide compound include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide and the like.

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 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone; quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone, etc.; 10-butyl-2-chloroacridone, benzil, methyl benzoylformate, titanocene compounds, and the like. These are preferably used in combination with a polymerization initiation aid (D1) (particularly an amine) described later.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 2 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be high and the exposure time tends to be short, so that the productivity of the color filter tends to be improved.

[5] polymerization initiation aid (D1)

The polymerization initiation aid (D1) is a compound or sensitizer for promoting the polymerization of a polymerizable compound whose polymerization is initiated by a polymerization initiator. When the polymerization initiator (D1) is contained, it is used in combination with the polymerization initiator (D).

Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds. Among them, a thioxanthone compound is preferable. It is also possible to use 2 or more polymerization initiation aids (D1) in combination.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N-dimethyl-p-toluidine, 4 '-bis (dimethylamino) benzophenone (commonly known as michelson), 4' -bis (diethylamino) benzophenone, and 4,4 '-bis (ethylmethylamino) benzophenone, and among them, 4' -bis (diethylamino) benzophenone is preferable. Commercially available products such as EAB-F (manufactured by Baotu chemical industries, Ltd.) may also be used.

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.

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

Examples of the carboxylic acid compound include phenylthioglycolic acid, methylphenylthioacetic acid, ethylphenylthioglycolic acid, methylethylphenylthioglycolic acid, dimethylphenylthioacetic acid, methoxyphenylthioglycolic acid, dimethoxyphenylthioglycolic acid, chlorophenylthioglycolic acid, dichlorophenylthioglycolic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioglycolic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

The content of the polymerization initiation aid (D1) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiation aid (D1) is within the above range, a blue pattern can be formed with further high sensitivity, and the productivity of the color filter tends to be improved.

[6] solvent (E)

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 having 2 to 4 carbon atoms of acetic acid.

Examples of the alkane diol diacetate having 4 to 6 carbon atoms include butane diol diacetate (also referred to as butanediol diacetate), pentane diol diacetate, and hexane diol diacetate. Examples of the butane diol diacetate include 1, 2-butane diol diacetate, 1, 3-butane diol diacetate, 1, 4-butane diol diacetate and 2, 3-butane diol diacetate, and 1, 3-butane diol diacetate is preferable, and 1, 4-butane diol diacetate is particularly preferable.

The content of the alkane diol diacetate having 4 to 6 carbon atoms is 1 to 20% by mass, preferably 1.5 to 18% by mass, more preferably 2 to 16% by mass, and still more preferably 2.5 to 14% by mass based on 100% by mass of the solvent. When the amount is within the above range, even after the colored curable resin composition is applied to a substrate, a certain fluidity can be secured, 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, the curing of the colored curable resin composition tends to be insufficient. Therefore, in a developing step of a method for manufacturing a color filter, which will be described later, a pattern is entirely or partially dissolved in a developer, and thus a desired colored coating film or a desired colored pattern may not be obtained.

The alkane diol diacetate may be a high boiling point solvent, and the boiling point of the alkane diol diacetate is preferably more than 150 ℃ and 300 ℃ or less, more preferably 160 ℃ or more, still more preferably 170 ℃ or more, still more preferably 180 ℃ or more, and particularly preferably 190 ℃ or more.

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.

Among these, the alkyl ester of acetic acid having 2 to 4 carbon atoms is more preferably n-butyl acetate or isobutyl acetate, and particularly preferably n-butyl acetate.

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

The content ratio of the C4-6 alkanediol diacetate to the C2-4 alkyl ester of acetic acid is preferably 0.02 to 1.0, more preferably 0.03 to 0.8, still more preferably 0.04 to 0.7, and still more preferably 0.05 to 0.5. When the amount is within the above range, the amount of adhesion of the colored coating film can be reduced even if the concentration of the colorant in the colored curable resin composition is high.

As described later, the solvent preferably further contains an ether ester solvent having a boiling point of 150 ℃ or lower.

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

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, pentyl 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.

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-II

Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

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, ethylene glycol monoethyl ether acetate, and the like, Diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate, and the like.

The ether ester solvent having a boiling point of 150 ℃ or lower is preferably propylene glycol monomethyl ether acetate or ethylene glycol monomethyl ether acetate, and particularly preferably propylene glycol monomethyl ether acetate.

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

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, and the like. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene, and the like. Examples of the amide solvent include N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone.

The content of the other solvent (E) (preferably an ether ester solvent, more preferably propylene glycol monomethyl ether acetate) is preferably 1 to 80% by mass, more preferably 1 to 70% by mass, even more preferably 2 to 60% by mass, and even more preferably 50% by mass or less or 40% by mass, based on 100% by mass of the solvent (E).

The content of the solvent (E) in the colored curable resin composition is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color density does not become insufficient at the time of forming a color filter, so that the display characteristics tend to become good.

[7] leveling agent (F)

The colored curable resin composition of the present invention may contain 1 or 2 or more kinds of leveling agents (F). Examples of the leveling agent (F) include a silicone surfactant (having no fluorine atom), a fluorine surfactant, and a silicone surfactant having a fluorine atom. These may have a polymerizable group in a side chain.

Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, 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 corporation), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by shin-Etsu chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF 46, TSF4452, and TSF4460 (manufactured by MOMENTIVE PERFORMANCIALS contract PAN).

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, examples thereof 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 (Co., Ltd.), F-top (registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi electro chemical Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Nitron (Co., Ltd.), and E5844 (manufactured by King Kogyo chemical Co., Ltd.).

Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, there may be mentioned MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477 and MEGAFAC F443 (manufactured by DIC Co., Ltd.).

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

[8] other Components

The colored curable resin composition of the present invention may contain 1 or 2 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-coagulation agent, an organic acid, an organic amine compound, and a curing agent, as required.

< method for producing colored curable resin composition >

The colored curable resin composition of the present invention can be prepared by mixing the colorant (a), the resin (B), the polymerizable compound (C), the polymerization initiator (D), the solvent (E), and, if necessary, the leveling agent (F), the polymerization initiation aid (D1), and other components.

< color filter and method for manufacturing the same, and display element

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 falls within the scope of the present invention. The color filter may also form a colored pattern.

The method for producing a colored pattern from the colored curable resin composition of the present invention includes photolithography, ink jet printing, printing and the like, and preferably photolithography. The photolithography method is a method in which a colored curable resin composition is applied to a substrate and dried to form a colored composition layer, and the colored composition layer is exposed to light through a photomask and developed. In the photolithography method, a colored coating film which is a cured product of the colored composition layer can be formed without using a photomask and/or without performing development at the time of exposure. The colored pattern and the colored coating film formed from 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.

As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass having a silica-coated surface, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, a substrate of silicon, a substrate having a thin film of aluminum, silver/copper/palladium alloy formed on the substrate, or the like can be used. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates. In addition, a substrate on which HMDS (1,1,1,3,3, 3-hexamethyldisilazane) treatment is performed on a silicon substrate may also be used.

The formation of each colored pixel by photolithography can be performed by a known or conventional apparatus and conditions. For example, the following can be used. First, a colored curable resin composition is applied onto a substrate, and is dried by heating (prebaking) and/or drying under reduced pressure to remove volatile components such as a solvent, thereby drying the composition to obtain a smooth colored composition layer. Examples of the coating method include a spin coating method, a slit coating method, and a slit spin coating method.

The temperature for the heat drying is preferably 30 to 120 ℃, and more preferably 50 to 110 ℃. The heating time is preferably 10 seconds to 5 minutes, and more preferably 30 seconds to 3 minutes. When the drying is carried out under reduced pressure, the drying is preferably carried out under a pressure of 50 to 150Pa and at a temperature of 20 to 25 ℃. The thickness of the colored composition layer is not particularly limited as long as it is appropriately selected according to the thickness of the target color filter.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the intended use is used. The light source used for the exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350nm may be cut off using a filter that cuts off the wavelength region, or light near 436nm, near 408nm, or near 365nm may be selectively extracted using a band-pass filter that extracts these wavelength regions. Specifically, the light source may be a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, or the like.

In order to uniformly irradiate parallel light rays to the entire exposure surface and perform precise alignment of the photomask and the substrate on which the colored composition layer is formed, an exposure device such as a mask aligner (proximity exposure machine) or a stepper (reduction projection exposure machine) is preferably used for exposure.

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

The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.

The developing method may be any of a paddle method, a dipping method, a spraying method, and the like. Further, the substrate is tilted at an arbitrary angle during development. After development, washing with water is preferred.

The obtained colored pattern is preferably subjected to post-baking. The post-baking temperature is preferably 80 to 250 ℃, more preferably 100 to 250 ℃, still more preferably 150 to 250 ℃, and still more preferably 160 to 235 ℃. The post-baking time is preferably 1 minute to 120 minutes, more preferably 2 minutes to 120 minutes, still more preferably 10 minutes to 60 minutes, and still more preferably 10 minutes to 30 minutes.

Since the thickness of the resulting colored pattern affects adjacent pixels, it is preferably as thin as possible. In particular, when the thickness is thick, light from the light source may leak through 2 or more pixels when the liquid crystal panel is manufactured, and when the panel is viewed obliquely, the vividness of the color may be lost. The thickness of the colored pattern after the postbaking is generally preferably 3 μm or less, more preferably 2.8 μm or less, and still more preferably 2.5 μm or less. The lower limit of the thickness of the colored pattern is not particularly limited, but is usually 0.1 μm or more, preferably 0.2 μm or more, and may be 0.5 μm or more or 1.0 μm or more. The colored curable resin composition of the present invention exhibits excellent developability during production of a colored pattern, and therefore is excellent as a material for a color filter.

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 a black matrix, and 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 is 0.71 or less.

In fig. 1, the color filter 1 is composed of a substrate 3, a black matrix 2, colored pixels (not shown), and the like, and the adhesion ratio is defined by the following equation.

The adhesion ratio of the color filter [ thickness of color filter on black matrix (a) ]/[ thickness of color filter on substrate (b) ])

In the present specification, the adhesion ratio can be defined as a value measured on a colored coating film formed first on a substrate.

The thickness of the color filter is 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 concave-convex shape, a tapered shape, or the like.

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 is, for example, 0.75 or less, preferably 0.74 or less, more preferably 0.73 or less, further preferably 0.72 or less, further preferably 0.71 or less, and exceeds 0, for example, 0.01 or more, or 0.1 or more.

The color filter of the present invention is useful as a color filter used for a display device such as a liquid crystal display device, an organic EL device, electronic paper, and the like, and a solid-state imaging device.

Examples

The curable resin composition of the present invention will be described below by way of specific examples, but the present invention is not limited to the following examples as long as the invention does not depart from the gist thereof. Unless otherwise specified, "part" means "part by mass" and "%" means "% by mass". In addition, the reaction was carried out under a nitrogen atmosphere if not otherwise specified.

The structure of the compound was confirmed by MASS analysis (LC; model 1200 by Agilent, MASS; LC/MSD by Agilent).

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin in terms of polystyrene were measured by GPC under the following conditions.

The device comprises the following steps: HLC-8120 GPC (manufactured by Tosoh corporation)

Column: TSK-GELG 2000HXL

Column temperature: 40 deg.C

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0mL/min

Concentration of solid component in test liquid: 0.001 to 0.01% by mass

Sample introduction amount: 50 μ L

A detector: RI (Ri)

Calibration standard substance: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

The ratio (Mw/Mn) of the weight average molecular weight to the number average molecular weight in terms of polystyrene obtained above was defined as the degree of dispersion (molecular weight distribution).

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 for neutralizing 1g of the resin.

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

The colored curable resin composition was applied by spin coating to a pattern of lines (corresponding to the black matrix of FIG. 1) formed with a thickness of 2.0 μmArray) of 2-inch square glass substrates (EAGLE 2000; manufactured by CORNING corporation). Thereafter, prebaking was carried out at 100 ℃ for 3 minutes to form a colored composition layer. After cooling, the resultant was exposed to an exposure apparatus (TME-150 RSK; manufactured by TOPCON, Inc.) at 20mJ/cm in an atmospheric air atmosphere²The exposure amount (365nm basis) of (b) is irradiated with light to the colored composition layer. After the light irradiation, postbaking was performed in an oven at 230 ℃ for 30 minutes, thereby obtaining 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 apparatus (DEKTAK 3; manufactured by Japan vacuum technology Co., Ltd.). The thickness of the colored coating film on the line pattern is a 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, and is set as (a), and the thickness of the colored coating film on the substrate is the thickness of the colored coating film on the glass substrate, and is set as (b), and the adhesion ratio is calculated.

[ Synthesis example 1]

An appropriate amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the atmosphere was changed to nitrogen, and 280 parts of propylene glycol monomethyl ether acetate was added and heated to 80 ℃ with stirring. Then, 38 parts of acrylic acid and 3, 4-epoxytricyclo [5.2.1.0 ] acrylic acid were added dropwise over 5 hours^2,6]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0^{2 ,6}]A mixed solution of 289 parts of a mixture of decane-9-yl esters (containing 1:1 ratio in terms of 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 completion of the dropwise addition, the mixture was held at 80 ℃ for 4 hours and then cooled to room temperature to obtain a copolymer (resin B1) solution containing 35.1% of a solid content and having a viscosity of 125 mPas as measured with a type B viscometer (23 ℃). The weight-average molecular weight Mw of the resulting copolymer was 9.2X 10³The dispersity (molecular weight distribution) was 2.08, and the acid value in terms of solid content was 77 mg-KOH/g. The resin (B1) has the following structural units.

[ preparation of Dispersion ]

As the dispersion liquid 1, a dispersion liquid containing the following components was used.

(Dispersion 1)

A dispersion liquid having a solid content of 21.5% and containing 4.8 parts of c.i. pigment red 291 (brominated diketopyrrolopyrrole), 17713.6 parts of c.i. pigment red, 1502.1 parts of c.i. pigment yellow, 6.4 parts of an acrylic dispersant (in terms of solid content), 7.9 parts of an acrylic resin (in terms of solid content), and 126.9 parts of propylene glycol monomethyl ether acetate.

(Dispersion 2)

A 22.7% solids dispersion containing 1500.9 parts of c.i. pigment yellow, 585.5 parts of c.i. pigment green, 1.2 parts of an acrylic dispersant (in terms of solid content), 2.5 parts of an acrylic resin (in terms of solid content), and 34.3 parts of propylene glycol monomethyl ether acetate.

(Dispersion 3)

A dispersion liquid containing 15.3 parts of C.I. pigment blue, 0.5 part of a compound represented by the formula (1-32), 1.3 parts of an acrylic dispersant (in terms of solid content), 1.0 part of an acrylic resin (in terms of solid content), and 20.9 parts of propylene glycol monomethyl ether acetate, wherein the solid content is 25.4%.

[ examples 1 to 3, comparative examples 1 to 6]

[ preparation of colored curable resin composition ]

Each of the components shown in table 2 was mixed to obtain each colored curable resin composition.

Colorant (a): dispersion 1 to 3 (numerical values in tables are amounts of dispersion used)

Resin (B): using resin (B1) (numerical values in the Table are amounts converted to solid contents)

Polymerizable Compound (C)

(C-1): dipentaerythritol polyacrylate (A-9550 APHA, manufactured by Newzhongcun chemical industry Co., Ltd.)

Polymerization initiator (D):

(D-1): irgacure (registered trademark) OXE-03; manufactured by BASF corporation; a compound represented by the formula (d 1-40)

Solvent (E):

(E-1): propylene glycol monomethyl ether acetate (hereinafter, also referred to as PGMA)

(E-2): 1, 4-Butanediodiacetic acid ester (hereinafter, also referred to as 1, 4-BGDA)

(E-3): butyl acetate (hereinafter, also referred to as BA)

Leveling agent (F):

(F-1): polyether-modified silicone oil (solid content conversion)

(Toray Silicone SH 8400; manufactured by Dow Corning Toray)

[ Table 2]

The obtained colored curable resin composition was evaluated by forming a color filter by the following method. The results are shown in Table 3.

< formation of color Filter (colored coating film) >

The colored curable resin composition was applied by spin coating onto a 2-inch square glass substrate (EAGLE 2000; manufactured by CORNING) on which a line pattern having a thickness of 2.0 μm was formed, and then prebaked at 100 ℃ for 3 minutes to form a colored composition layer. After cooling, the resultant was exposed to an exposure apparatus (TME-150 RSK; manufactured by TOPCON, Inc.) at an atmospheric pressure of 20mJ/cm²The exposure amount (365nm basis) of (b) is irradiated with light to the colored composition layer. After the light irradiation, post-baking was performed at 230 ℃ for 30 minutes in an oven, thereby obtaining a colored coating film. After cooling, the thickness of the resulting colored coating film on the glass substrate and the thickness of the resulting colored coating film on the line pattern were measured by a thickness measuring apparatus (DEKTAK3, manufactured by Japan vacuum technology, Ltd.). The thickness and adhesion rate of the colored coating film are shown in table 3.

[ Table 3]

In examples 1 to 3, the adhesion rate was reduced as compared with comparative examples 1 to 6, and therefore, if a color filter or the like is produced from the colored curable resin composition of the present invention, improvement in yield can be expected.

Industrial applicability

The colored curable resin composition of the present invention is extremely useful industrially because it can form a colored coating film having a reduced adhesion rate and can improve the yield of color filters, display devices, solid-state imaging elements, and the like.

Description of the symbols

1: color filter

2: black matrix

3: substrate

a: thickness of color filter on black matrix

b: thickness of color filter on substrate

Claims (8)

1. A colored curable resin composition characterized by comprising a colorant, a resin, a polymerizable compound, a polymerization initiator and a solvent,

the solvent at least comprises alkane diol diacetate with 4-6 carbon atoms and alkyl ester with 2-4 carbon atoms of acetic acid,

the content of the C4-6 alkanediol diacetate is 1 to 20% by mass based on 100% by mass of the solvent.

2. The colored curable resin composition according to claim 1, wherein the content ratio of the C4-6 alkane diol diacetate to the C2-4 alkyl ester of acetic acid is 0.02-1.0.

3. The colored curable resin composition according to claim 1 or 2, wherein the solvent further comprises an ether ester solvent having a boiling point of 150 ℃ or lower.

4. The colored curable resin composition according to any one of claims 1 to 3, wherein the content of the colorant is 10 to 55% by mass in 100% by mass of the solid content of the colored curable resin composition, and the colorant contains 1 or more selected from a red pigment, a green pigment and a blue pigment.

5. A color filter comprising the colored curable resin composition according to any one of claims 1 to 4.

6. A color filter formed by forming a pattern on a substrate and partially overlapping a black matrix, wherein 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 is 0.71 or less.

7. A display device comprising the color filter of claim 5 or 6.

8. A solid-state imaging element comprising the color filter according to claim 5 or 6.

Images