KR20220042170A - colored curable resin composition - Google Patents

Abstract

[PROBLEMS] An object of the present invention is to provide a colored curable resin composition capable of forming a colored coating film having a reduced loading rate of the colored coating film on a black matrix.
[Solution means] a colorant, a resin, a polymerizable compound, a polymerization initiator, and a solvent, wherein 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, Content rate of C4-C6 alkanediol diacetate is 1 mass % or more and 20 mass % or less in 100 mass % of solvent, Colored curable resin composition characterized by the above-mentioned.

Description

colored curable resin composition

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

[0002] As a colored curable resin composition for forming a color filter included in a display device or a solid-state image sensor, there is known a colored curable resin composition containing a colorant, a binder resin, a polymerizable compound, a polymerization initiator, and a solvent (Patent Document 1) and 2).

Japanese Patent Laid-Open No. 2009-091551 Japanese Patent Laid-Open No. 2010-044285

[0004] A color filter is constituted by a substrate, each color pixel, and a black matrix formed on the substrate and intersecting each color pixel or the like.

From the viewpoint of preventing light leakage, the ends of each colored pixel are usually formed so as to overlap on a black matrix, but on the other hand, a colored coating film of each colored pixel existing on the black matrix. When the colorant concentration is increased in a color filter requiring high color reproducibility, it is easy to form ridges, and the loading amount of the colored coating film on the black matrix (hereinafter also referred to as loading rate) ) was desired to be reduced.

The objective of this invention is providing the colored curable resin composition which can form the colored coating film by which the loading rate of the colored coating film on a black matrix was reduced.

[0005] The present invention provides a colored curable resin composition, a color filter, a display device, and a solid-state image sensor shown below.

[0006] [1] contains a colorant, a resin, a polymerizable compound, a polymerization initiator, and a solvent,

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

Content rate of said C4-C6 alkanediol diacetate is 1 mass % or more and 20 mass % or less in 100 mass % of solvent, Colored curable resin composition characterized by the above-mentioned.

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

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

[4] The content of the colorant is 10 mass% or more and 55 mass% or less in 100 mass% of the solid content of the colored curable resin composition, and the colorant is a red pigment, a green pigment, and a blue pigment. The colored curable resin composition in any one of [1]-[3] containing 1 or more types chosen from (群).

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

[6] A color filter formed by pattern formation on a substrate and partially overlapping a black matrix, wherein a ratio between the thickness (b) of the color filter on the substrate and the thickness (a) of the color filter on the black matrix [(a) )/(b)], a color filter characterized in that the loading rate is 0.71 or less.

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

[8] A solid-state imaging device 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 with a reduced loading rate of the colored coating film on a black matrix.

Moreover, according to this invention, the yield in manufacture of a color filter, a display apparatus, a solid-state image sensor, etc. improves.

1 is a diagram showing a loading rate expressed as a ratio [(a)/(b)] of a thickness (a) of a color filter on a black matrix to a thickness (b) of a color filter on a substrate; am.

[0009] The colored curable resin composition of the present invention includes a colorant (hereinafter, may be referred to as a colorant (A)), a resin (hereinafter may be referred to as a resin (B)), a polymerizable compound (hereinafter, may be referred to as a colorant (B).) Contains 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).) do.

The colored curable resin composition of this invention may contain the polymerization initiation adjuvant (Hereinafter, it may be called polymerization initiation adjuvant (D1).).

The colored curable resin composition of this invention may contain the leveling agent (Hereinafter, it may call a leveling agent (F).).

[0010] [1] Colorant (A)

The colored curable resin composition of this invention contains a coloring agent (A). It is preferable that at least 1 sort(s) chosen from the group which consists of dye and a pigment is included, and, as for a coloring agent (A), it is more preferable that a pigment is included. The coloring agent (A) may contain 1 type(s) or 2 or more types.

[0011] [Pigment]

As a pigment, an organic pigment and an inorganic pigment are mentioned, The compound classified into the pigment by the color index (The Society of Dyers and Colorists publication) is mentioned. A pigment can be used individually or in combination of 2 or more types.

[0012] As the pigment, 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 yellow pigments;

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

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 other red pigments;

C.I. Blue pigments, such as pigment blue 15, 15:3, 15:4, 15:6, 60;

C.I. Violet pigments, such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;

C.I. Green pigments, such as Pigment Green 7, 36, 58, 59;

C.I. Brown pigments, such as Pigment Brown 23 and 25;

C.I. Black pigments, such as Pigment Black 1 and 7, etc. are mentioned.

[0013] Pigments, if necessary, rosin (rosin) treatment, surface treatment using a pigment derivative introduced with an acidic or basic group, graft treatment to the pigment surface with a polymer compound, etc., sulfuric acid atomization method (微粒化method) Atomization treatment by such as, washing treatment with an organic solvent or water for removing impurities, removal treatment by ion exchange method of ionic impurities, etc. may be performed. It is preferable that the particle diameters of a pigment are respectively uniform.

[0014] The pigment can be made into a pigment dispersion in a state uniformly dispersed in a pigment dispersant solution by containing a pigment dispersant and performing a dispersion treatment. A pigment may be disperse|distributed independently, respectively, and may mix and disperse|distribute multiple types.

[0015] Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigment dispersants. These pigment dispersants may be used independently and may be used in combination of 2 or more type. As a pigment dispersant, as a brand name, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Florene (manufactured by KYOEISHA CHEMICAL Co., LTD.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF Co., Ltd.) ), Ajispar (manufactured by Ajinomoto Fine-Techno Co., Inc.), Disperbyk (manufactured by BYK-Chemie), and the like.

[0016] When a pigment dispersant is used, the amount used is preferably 100 parts by mass or less, and more preferably 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the pigment. When the usage-amount of a pigment dispersant exists in said range, there exists a tendency for the pigment dispersion liquid of a uniformly dispersed state to be obtained.

[0017] The colorant (A) preferably includes at least one selected from the group consisting of a red pigment, a green pigment, and a blue pigment, and preferably further includes a yellow pigment from the viewpoint of chromaticity adjustment.

[0018] The red pigment is, among the pigments, C.I. More preferably, it contains at least any one of Pigment Red 144, 177, 242, 254, 269 and 291, azo pigment, diketopyrrolopyrrole pigment (synonymous with CI Pigment Red 291), anthraquinone pigment, chromium It is more preferable to include at least one of a santhene pigment and a perylene pigment, and CI It is particularly preferred to include at least any one of Pigment Red 177 and 291. You may use this red pigment together with a yellow pigment, an orange pigment, etc.

[0019] The green pigment is, among the pigments, C.I. It is more preferable to include at least any one of Pigment Green 58 and 59. You may use this green pigment together with a yellow pigment.

[0020] The blue pigment is, among the pigments, C.I. It is more preferable to include at least any one of Pigment Blue 15, 15:3, 15:4 and 15:6, and C.I. Particular preference is given to at least comprising Pigment Blue 15:6. A blue pigment may use together with a violet color pigment, and may use it together with the dye mentioned later.

[0021] The yellow pigment is, among the pigments, C.I. It is more preferable to include at least any one of Pigment Yellow 129, 138, 139, 150, 185 and 231, and it is more preferable to include at least any one of a quinophthalone pigment, a metal-containing pigment, and an isoindoline pigment, , CI It is especially preferable to contain at least Pigment Yellow 150.

[0022] [dye]

As the dye, known dyes can be used, and solvent dyes, acid dyes, direct dyes, mordant dyes, etc. are mentioned, for example, solvent, acid, basic, reactive in Color Index (published by The Society of Dyers and Colorists) Compounds classified as dyes such as , direct, disperse, mordant, or vat, or dye notes (SHIKISENSHA CO., LTD. and the known dyes that have been described. What is necessary is just to select dye suitably according to the spectral spectrum of a desired color filter. These dyes may be used independently and may use 2 or more types together. The dye is preferably an organic solvent-soluble dye.

[0023] As a specific example of the dye, 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, 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 Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. C.I. solvent dyes,

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, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;

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, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340;

C.I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, CIs of 104, 105, 106, 109, etc. acid dye,

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, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. C.I. direct dye,

C.I. Disperse Yellow 51, 54, 76;

C.I. Disperse Violet 26, 27;

C.I. Disperse Blue 1, 14, 56, 60, etc. C.I. dispers dye,

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 Green 1, etc. C.I. basic dye,

C.I. Reactive Yellow 2, 76, 116;

C.I. Reactive Orange 16;

C.I. Reactive Red 36 and other C.I. reactive dyes,

C.I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

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

C.I. Modern 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. Mordant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53, etc. C.I. modern dye,

C.I. C.I. of vat green 1 etc. Vat dye etc. are mentioned.

In addition, as the dye, according to the chemical structure, triarylmethane dye, xanthene dye, azo dye, cyanine dye, triphenylmethane dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine Dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, tetraazaporphyrin dyes, etc. are mentioned.

[0025] The dye is preferably the following dyes (A1) to (A4).

[0026] [Dye (A1)]

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

[0027]

[0028] In the formula (A-IV), R ^1A to R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a sulfonyl group, a hydroxy group, or a saturated hydrocarbon group having 1 to 20 carbon atoms, and the saturated An oxygen atom may be inserted between the methylene groups constituting the hydrocarbon group.

R ^9A to R ^12A each independently represent a hydrogen atom, an optionally substituted aryl group having 6 to 20 carbon atoms, an optionally substituted aralkyl group having 7 to 20 carbon atoms, or a saturated hydrocarbon group having 1 to 20 carbon atoms, The aryl group and the substituent which the aralkyl group may have may be -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , and an oxygen atom may be inserted between the methylene groups constituting the saturated hydrocarbon group. , The 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 ^9A and R ^10A may combine to form a ring together with the nitrogen atom to which they are bonded, or R ^11A and R ^12A may combine to form a ring together with the nitrogen atom to which they are bonded.

A represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent or an aromatic heterocyclic group having 3 to 20 carbon atoms which may have a substituent, and the aromatic hydrocarbon group and the substituent which the aromatic heterocyclic group may have are - SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f may be used.

[Y] ^(mn)- represents an anion having an arbitrary (mn) valence.

m represents any natural number.

n represents the number of -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f having as a substituent, and is 0 or 1.

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

[0029] The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^1A to R ^12A may be any of linear, branched and cyclic, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, or a pen. and a tyl group, a hexyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group, an icosyl group, a cyclohexyl group, and an adamantyl group.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^1A to R ^12A and having an oxygen atom inserted between the methylene groups constituting the saturated hydrocarbon group include groups represented by the following formulas. In the following formula, * represents a bond with a carbon atom or a nitrogen atom.

Among them, a saturated hydrocarbon group having 1 to 10 carbon atoms, in which an oxygen atom is inserted between methylene groups constituting the saturated hydrocarbon group, is preferable, and is a saturated hydrocarbon group having 1 to 6 carbon atoms, a methylene group constituting the saturated hydrocarbon group. A group with an oxygen atom inserted therebetween is more preferable.

[0031]

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

Examples of the aralkyl group having 7 to 20 carbon atoms in R ^9A to R ^12A include a benzyl group, a phenylethyl group, and a methylphenylethyl group.

Examples of the amino group which may have a substituent in R ^9A to R ^12A include an amino group having one alkyl group having 1 to 4 carbon atoms, such as a methylamino group and an ethylamino group; an amino group having two alkyl groups having 1 to 4 carbon atoms, such as a dimethylamino group, a diethylamino group, and an ethylmethylamino group; An amino group etc. are mentioned.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms in R ^9A to R ^12A having a halogen atom or an optionally substituted amino group include a trifluoromethyl group, a trifluoroethyl group, a chloroethyl group, a bromoethyl group, and an iodine group. and an ethyl group, N,N-dimethylaminoethyl group, pentafluoropropyl group, chlorohexyl group, bromohexyl group, iodinehexyl group, and N,N-dimethylaminohexyl group.

[0033] In the aryl group which may have a substituent and the aralkyl group which may have a substituent represented by R ^9A to R ^12A , as the substituent, -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R In addition to ^f , halogen atoms, such as a fluorine atom, a chlorine atom, and an iodine atom; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; hydroxyl group; sulfo group; sulfamoyl group; A C1-C6 alkylsulfonyl group, such as a methylsulfonyl group, etc. are mentioned.

Examples of the fluoroalkyl group having 1 to 12 carbon atoms represented by R ^f include a trifluoromethyl group and a 2,2,2-trifluoroethyl group.

Specific examples of the aryl group which may have a substituent and the aralkyl group which may have a substituent include a group represented by the following formula. In the following formula, * represents a bond with a nitrogen atom.

[0035]

[0036]

[0037]

[0038] Examples of the ring formed by bonding R ^9A and R ^10A together with the nitrogen atom to which they are bonded and the ring formed by bonding of R ^11A and R ^12A together with the nitrogen atom to which they are bonded include a pyrrolidine ring and a morpholine ring. , a piperidine ring, a piperazine ring, and the like.

[0039] R ^1A to R ^8A are each independently preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, and each independently a hydrogen atom, a methyl group, It is more preferable that it is a fluorine atom or a chlorine atom.

[0040] R ^9A to R ^12A are preferably, each independently, 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 a substituted group from the viewpoint of ease of synthesis. It is an aryl group having 6 to 20 carbon atoms which may be formed, and more preferably, each independently 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 optionally substituted C 6 to carbon group. 12 is an aryl group, and the aralkyl group and the hydrogen atoms contained in the aryl group are 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 alkyl sulfo group having 1 to 4 carbon atoms. It may be substituted with a phonyl group, and more preferably, each independently is an alkyl group having 1 to 8 carbon atoms, a phenyl group or a benzyl group, and the hydrogen atom contained in the phenyl group and the benzyl group is a halogen atom or a halo group having 1 to 4 carbon atoms. It may be substituted with an alkyl group, a C1-C4 alkoxy group, a hydroxyl group, a sulfo group, or a C1-C4 alkylsulfonyl group. As such a phenyl group or a benzyl group, the group represented by a following formula is mentioned. In the following formula, * represents a bond with a nitrogen atom.

[0041]

[0042]

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

Examples of the aromatic hydrocarbon group which may have a substituent represented by A include a group represented by the following formula. * indicates a bond with a carbon atom.

[0044]

[0045] The aromatic heterocyclic group representing A means an aromatic group having at least one hetero atom as a component of the ring. As a hetero atom, a nitrogen atom, an oxygen atom, a sulfur atom, etc. are mentioned.

[0046] A is preferably an aromatic heterocyclic group having at least one nitrogen atom as a component of the ring. Examples of the aromatic heterocyclic group include a 5-membered aromatic heterocyclic group 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 6-membered aromatic heterocyclic group having a nitrogen atom, such as a pyridyl group, a pyridinyl group and a pyridazinyl group; Condensed ring aromatic heterocyclic groups, such as a benzimidazolyl group and an indolyl group, are mentioned.

Examples of the substituent in A include a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a sulfo group, a sulfamoyl group, an alkylsulfonyl group having 1 to 6 carbon atoms, and an amino group which may have a substituent, and specifically may include the same substituents as those exemplified by R ^9A to R ^12A .

A is preferably a group represented by the formula (t1).

[0048]

[0049] [In formula (t1),

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

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

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

R ⁴⁵ and R ⁴⁶ are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 7 to carbon atoms which may have a substituent 30 represents an aralkyl group, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, -CH ₂ - contained in the saturated hydrocarbon group may be substituted with at least one of -O- and -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent -CH ₂ - is not simultaneously substituted with -O-, and the terminal -CH ₂ - is not substituted with -O- or -CO-. R ⁴⁵ and R ⁴⁶ may combine to form a ring together with the nitrogen atom to which they are bonded.

* indicates a bond with a carbocation.]

Examples of the aromatic heterocyclic group which may have a substituent representing A include a group represented by the following formula. * represents a bond with a carbon atom.

[0051]

[0052] X2 is preferably -S-.

It is preferable that it is a C6-C20 aromatic hydrocarbon group which may have a substituent, and, as for R< ⁵⁶ >, it is more preferable that it is a phenyl group which may have a substituent.

R ⁴⁵ and R ⁴⁶ are each independently preferably 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, and may have 1 to carbon atoms which may have a substituent. More preferably, it is an alkyl group having ∼6 or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, one of which is an alkyl group having 1 to 6 carbon atoms which may have a substituent, and the other has a substituent It is more preferable that it is a C6-C12 aromatic hydrocarbon group which may exist.

A is preferably a group represented by formulas (A1-12) and (A1-13).

[0053] [Y] ^(mn)- includes a known anion, but from the viewpoint of heat resistance, a boron-containing anion, an aluminum-containing anion, a fluorine-containing anion, and a group consisting of tungsten, molybdenum, silicon and phosphorus An anion containing at least one element selected from and oxygen is preferred.

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

[0055]

[0056] In formula (4), W ¹ and W ² each independently have at least two monovalent proton-donating substituents, and two substituents formed by releasing protons from the group The branch represents the group. M represents a boron atom or an aluminum atom.]

[0057] A group having at least two monovalent proton-donating substituents, and having two substituents formed by releasing protons from the group, is from a compound having at least two monovalent proton-donating substituents (eg, hydroxyl group, carboxyl group, etc.) and groups in which a proton is released from each of the two proton-donating substituents. As the compound, preferably catechol 2,3-dihydroxynaphthalene, 2,2'-biphenol, 3-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-hydroxy and hydroxy-2-naphthoic acid, binaphthol, salicylic acid, benzylic acid, or mandelic acid, which may have a substituent.

[0058] 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; nitro group; hydroxyl group; An amino group is mentioned.

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

[0060]

[wherein, R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are each independently a hydrogen atom, a hydroxy group, an amino group, a nitro group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or halo having 1 to 4 carbon atoms. represents an alkyl group or an alkoxy group having 1 to 4 carbon atoms.]

[0062] For example, the anion (BC-1) to the anion (BC-28) described below are exemplified. M represents a boron atom or an aluminum atom. tBu in Table 1 represents a tert-butyl group.

[0063] [Table 1]

[0064]

[0065]

[0066]

[0067]

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

[0069]

[0070] In formula (6), W ³ and W ⁴ each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or W ³ and W ⁴ are bonded to each other to represent a fluorine atom having 1 to 4 carbon atoms Forms an alkanediyl group.]

[0071]

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

[0073]

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

[0075]

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

[0077] As the fluorinated alkyl group having 1 to 4 carbon atoms each represented by W ³ to W ⁷ in formulas (6) and (7), a perfluoroalkyl group is preferable, for example, -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF(CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF(CF ₃ ) ₂ , -C(CF ₃ ) ₃ , and the like.

[0078] As the fluorinated alkanediyl group having 2 to 4 carbon atoms formed by bonding W ³ and W ⁴ in the formula (6), a perfluoroalkanediyl group is preferable, for example, -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ CF ₂ -, and the like.

[0079] As the fluorinated alkanediyl group having 1 to 4 carbon atoms represented by Y ¹ in the formula (8), a perfluoroalkanediyl group is preferable, for example, -CF ₂ -, -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ -, -C(CF ₃ ) ₂ -, -CF ₂ CF ₂ CF ₂ CF ₂ -, and the like.

[0080] The fluorinated alkyl group having 1 to 4 carbon atoms represented by Y ² in Formula (9) is preferably a perfluoroalkyl group, -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , - CF(CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF(CF ₃ ) ₂ , -C(CF ₃ ) ₃ , and 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).

[0082]

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

[0084]

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).

[0086]

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

[0088]

[0089] [Y] ^(mn)- is preferably an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen. As [Y] ^(mn)- containing tungsten, the anion of heteropolyacid or isopolyacid is preferable, and the anion of tungstophosphoric acid, tungstosilicic acid, and tungsten-type isopolyacid is more preferable.

[0090] As such an anion of heteropolyacid or isopolyacid containing tungsten, Keggin type tungstophosphate ion α-[PW ₁₂ O ₄₀ ] ^3- , Dawson type tungstophosphate ion α-[ P ₂ W ₁₈ O ₆₂ ] ^6- , β-[P ₂ W ₁₈ O ₆₂ ] ^6- , Kegin-type tungstosilicate ion α-[SiW ₁₂ O ₄₀ ] ^4- , β-[SiW ₁₂ O ₄₀ ] ^4- , γ-[SiW ₁₂ O ₄₀ ] ^4- may be mentioned, and further examples include [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ ] O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , α-[SiW ₉ O ₃₄ ] ^10- , γ-[SiW ₁₀ O ₃₆ ] ^8- , α-[SiW ₁₁ O ₃₉ ] ^8- , β-[SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- , and the like.

[0091] Examples of the anion composed of at least one element selected from the group consisting of silicon and phosphorus and oxygen include SiO ₃ ^2- and PO ₄ ^3- .

[0092] In particular, from the viewpoint of the ease of synthesis and post-treatment, heteropolyacid anions such as Keggin type tungstophosphate ion, Dawson type tungstophosphate ion, Keggin type tungstosilicate ion, [W ₁₀ O ₃₂ ] ^4- , etc. of isopolyacid anion is preferred.

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

[0094]

[0095]

[0096]

[0097]

[0098]

[0099] The dye (A1) preferably includes a salt represented by the formula (A-IV-26).

[0100] In the case of having a sulfo group (-SO ₃ H) as a substituent, a salt may be formed by exchanging an arbitrary cation with a hydron. As arbitrary cations, an alkali metal ion, an organic ammonium ion, the imidazolium ion which may have a substituent, etc. are mentioned. When it has two or more sulfo groups, you may form a salt with the metal ion of divalent or more.

[0101] [Dye (A2)]

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

[0102] The xanthene dye (A2) is a dye containing a compound having a xanthene skeleton in a molecule. As the xanthene dye (A2), for example, C.I. Acid Red 51 (hereinafter, the description of C.I. Acid Red will be omitted and only the number will be described. The same applies to 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. Modern Red 27, C.I. Reactive Red 36 (Rose Bengal B), sulforodamine G, the xanthene dye of Unexamined-Japanese-Patent No. 2010-32999, the xanthene dye of Unexamined-Japanese-Patent No. 4492760, etc. are mentioned. It is preferable to dissolve in an organic solvent.

[0103] Among these, as the xanthene dye (A2), a dye containing the compound represented by the formula (1a) (hereinafter sometimes referred to as “compound (1a)”) is preferable. Compound (1a) may be a tautomer thereof. When using compound (1a), content of compound (1a) in xanthene dye (A2) becomes like this. Preferably it is 50 mass % or more, More preferably, it is 70 mass % or more, More preferably, it is 90 mass % or more. In particular, as the xanthene dye (A2), it is preferable to use only the compound (1a).

[0104]

[0105] In formula (1a), R ^1a to R ^4a are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or 6 to 10 carbon atoms which may have a substituent A monovalent aromatic hydrocarbon group is represented, and -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -O-, -CO- or -NR ^11a -. R ^1a and R ^2a may together form a ring containing a nitrogen atom, and R ^3a and R ^4a may together form a ring containing a nitrogen atom.

R ^5a is -OH, -SO ₃ ^- , -SO ₃ H, -SO _{3 -Za} ⁺ , -CO ₂ H, -CO ₂ ^- Za ⁺ , -CO ² R ^8a , -SO ₃ R ^8a or -SO ₂ NR ^9a R ^10a is represented.

R ^6a and R ^7a each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

m represents the integer of 0-5. When m is 2 or more, a plurality of R ^5a may be the same or different.

a represents the integer of 0 or 1.

Xa represents a halogen atom.

Za ⁺ represents ⁺ N(R ^11a ) ₄ , Na ⁺ or K ⁺ , and four R ^11a may be the same or different.

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

R ^9a and R ^10a each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated hydrocarbon group is -O-, -CO- , -NH- or -NR ^8a - may be substituted, and R ^9a and R ^10a may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom.

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

[0106] In Formula (1a), when -SO ₃ ^- exists, the number is one.

[0107] Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^1a to R ^4a include a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group.

[0108] Examples of the substituent that the aromatic hydrocarbon group may have include a halogen atom, a carboxyl group, -R ^8a , -OH, -OR ^8a , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Za ⁺ , -CO ₂ H , -CO ₂ R ^8a , -SR ^8a , -SO ₂ R ^8a , -SO ₃ R ^8a or -SO ₂ NR ^9a R ^10a .

Among these, as a substituent, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Za ⁺ and -SO ₂ NR ^9a R ^10a are preferable, and -SO ₃ ^- Za ⁺ and -SO ₂ NR ^9a R ^10a are more preferable. desirable. As -SO ₃ ^- Za ⁺ in this case, -SO ₃ ^{- +} N(R ^11a ) ₄ is preferable.

[0109] Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ^1a to R ^4a and R ^8a to R ^11a include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group; straight-chain alkyl groups such as octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group and icosyl group; branched alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a cyclodecyl group.

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

The hydrogen atom included in the saturated hydrocarbon group in R ^9a and R ^10a may be substituted with, for example, a hydroxyl group or a halogen atom.

[0110] Examples of the ring formed by R ^1a and R ^2a together and the ring formed by R ^3a and R ^4a together include the following.

[0111]

[0112] As -OR ^8a , for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, an icosyloxy group, etc. can be heard

[0113] Examples of -CO ₂ R ^8a include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

[0114] Examples of -SR ^8a include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.

Examples of -SO ₂ R ^8a include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.

Examples of -SO ₃ R ^8a include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

[0115] -SO ₂ NR ^9a As R ^10a , for example, a sulfamoyl group;

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

N,N-dimethylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-propylmethylsulfamoyl group, N,N-isopropylmethylsulfamoyl group, N such as N,N-tert-butylmethylsulfamoyl group, N,N-butylethylsulfamoyl group, N,N-bis(1-methylpropyl)sulfamoyl group, N,N-heptylmethylsulfamoyl group, An N-2 substituted sulfamoyl group etc. are mentioned.

[0116] R ^5a is preferably -CO ₂ H, -CO ₂ ^{-Za +} , -CO ₂ R ^8a , -SO ₃ ^- , -SO ₃ ^{-Za +} , -SO ₃ H or -SO ₂ NHR ^9a , -SO ₃ ^- , -SO ₃ ^{-Za +} , -SO ₃ H or -SO ₂ NHR ^9a are more preferable.

1-4 are preferable and, as for m, 1 or 2 are more preferable.

[0117] Examples of the alkyl group having 1 to 6 carbon atoms in R ^6a and R ^7a include those having 1 to 6 carbon atoms among the alkyl groups exemplified above.

[0118] Examples of the aralkyl group having 7 to 10 carbon atoms in R ^11a include a benzyl group, a phenylethyl group, and a phenylbutyl group.

[0119] Za ⁺ is ⁺ N(R ^11a ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ^11a ) ₄ .

The ⁺ N(R ^11a ) ₄ is preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms in at least two of the four R ^11a groups. Moreover, 20-80 are preferable and, as for total carbon number of four ^R11a , 20-60 are more preferable.

[0120] As the compound (1a), a compound represented by the formula (2a) (hereinafter sometimes referred to as “compound (2a)”) is preferable. Compound (2a) may be a tautomer thereof.

[0121]

[In formula (2a), R ^21a to R ^24a each independently represent a hydrogen atom, —R ^26a or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. R ^21a and R ^22a may together form a ring containing a nitrogen atom, and R ^23a and R ^24a may together form a ring containing a nitrogen atom.

R ^25a represents -SO ₃ ^- , -SO ₃ H, -SO ₃ ^{-Z1 +} or -SO ₂ NHR ^26a .

m1 represents the integer of 0-5. When m1 is 2 or more, a plurality of R ^25a may be the same or different.

a1 represents the integer of 0 or 1.

X1 represents a halogen atom.

R ^26a represents a halogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a carboxy group.

Z1 ⁺ represents ⁺ N(R ^27a ) ₄ , Na ⁺ or K ⁺ , and four R ^27a may be the same or different.

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

[0122] Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms for R ^21a to R ^24a include the same groups as those exemplified as the aromatic hydrocarbon group for R ^1a to R ^4a . The hydrogen atom contained in this aromatic hydrocarbon group may be substituted by -SO ₃ ^- , -SO ₃ H, -SO ₃ ^{-Z1 +} , -SO ₃ R ^26a , or -SO ₂ NHR ^26a .

As a combination of R ^21a to R ^24a , R ^21a and R ^23a are each independently a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms (the saturated hydrocarbon group may have a halogen atom or a carboxy group), R ^22a and R ^24a is a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atoms included in the aromatic hydrocarbon group are -SO ₃ ^- , -SO ₃ H, -SO ₃ ^{-Z1 +} , -SO ₃ R ^26a or -SO It is preferably substituted with ₂ NHR ^26a . A more preferred combination is that R ^21a and R ^23a are, independently of each other, a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (the alkyl group may have a halogen atom or a carboxy group.), and R ^22a and R ^24a are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. 10 is a monovalent aromatic hydrocarbon group, wherein a hydrogen atom contained in the aromatic hydrocarbon group is substituted with -SO ₃ ^{-Z1 +} or -SO ₂ NHR ^26a .

[0123] As a ring containing a nitrogen atom formed together by R ^21a and R ^22a , and a ring containing a nitrogen atom formed together by R ^23a and R ^24a , the same as the ring formed by R ^1a and R ^2a together thing can be heard Especially, an aliphatic heterocyclic ring is preferable. Examples of the aliphatic heterocycle include the following.

[0124]

[0125] Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms for R ^26a and R ^27a include the same groups as those exemplified as the saturated hydrocarbon group for R ^8a to R ^11a .

When R ^21a to R ^24a are -R ^26a , it is preferable that -R ^26a is each independently a methyl group or an ethyl group. In addition, as R ^26a in -SO ₃ R ^26a and -SO ₂ NHR ^26a , a branched chain alkyl group having 3 to 20 carbon atoms is preferable, more preferably a branched chain alkyl group having 6 to 12 carbon atoms, and 2-ethyl A hexyl group is more preferable.

[0126] Z1 ⁺ is ⁺ N(R ^27a ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ^27a ) ₄ .

As said ⁺ N( ^R27a ) ₄ , it is preferable that at least 2 among four ^R27a are C5-C20 monovalent|monohydric saturated hydrocarbon groups. Moreover, 20-80 are preferable and, as for total carbon number of four ^R27a , 20-60 are more preferable.

[0127] m1 is preferably 1 to 4, more preferably 1 or 2.

[0128] Further, as the compound (1a), a compound represented by the formula (3a) (hereinafter sometimes referred to as “compound (3a)”) is also preferable. Compound (3a) may be a tautomer thereof.

[0129]

[0130] [In formula (3a), R ^31a and R ^32a each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is an aromatic hydrocarbon having 6 to 10 carbon atoms. It may be substituted with a group, a carboxy 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, -CH ₂ - contained in the saturated hydrocarbon group is -O-, - It may be substituted with CO- or -NR ^11a -.

R ^33a and R ^34a each independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.

R ^31a and R ^33a may together form a ring containing a nitrogen atom, and R ^32a and R ^34a may together form a ring containing a nitrogen atom.

p and q each independently represent the integer of 0-5. When p is 2 or more, some R ^33a may be same or different, and when q is 2 or more, some R ^34a may be same or different.

R ^11a has the same meaning as above.]

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ^31a and R ^32a include a group having 1 to 10 carbon atoms among those in R ^8a .

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be included as a substituent include the same groups as those for R ^1a .

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

It is preferable that R ^31a and R ^32a each independently represent a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms (the saturated hydrocarbon group may have a halogen atom or a carboxy group).

[0132] Examples of the alkyl group having 1 to 4 carbon atoms in R ^33a and R ^34a include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. there is.

Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ^33a and R ^34a include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group and an isopropylsulfanyl group.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ^33a and R ^34a include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group and an isopropylsulfonyl group.

R ^33a and R ^34a are preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

[0133] As for p and q, an integer of 0 to 2 is preferable, and 0 or 1 is preferable.

[0134] Examples of the compound (1a) include compounds represented by formulas (1-1) to (1-107). In the formula, R ^40a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group. R ^26a has the same meaning as in Formula (2a).

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154] Among the above compounds, represented by formulas (1-1) to (1-23), (1-37) to (1-85) and (1-102) to (1-107), The compound represented by Formula (2a) corresponds to Compound (2a), and the compound represented by Formulas (1-24) to Formula (1-36) and Formula (1-86) to Formula (1-101) corresponds to Compound (3a). .

Among these, C.I. The sulfonamidide of Acid Red 289, C.I. The quaternary ammonium salt of Acid Red 289, C.I. Sulfonamides of Acid Violet 102 or C.I. The quaternary ammonium salt of Acid Violet 102 is preferred. As such a compound, the compound etc. which are represented by Formula (1-1) - Formula (1-8), Formula (1-11), and Formula (1-12) are mentioned, for example.

[0155] Further, compounds represented by formulas (1-24) to (1-33) are also preferable from the viewpoint of excellent solubility in organic solvents.

From the viewpoint of improving the chromaticity range and transmittance of the resulting coating film, compounds represented by formulas (1-32), (1-44) and (1-97) are also preferable.

[0156] Xanthene dye (A2) is a commercially available xanthene dye (eg, "Chugai Aminol Fast Pink RH/C" manufactured by Chugai Kasei Company, Limited, "Rhodamin 6G" manufactured by Taoka Chemical Company, Limited) ) can be used. In addition, by using a commercially available xanthene dye as a starting material, it can also be synthesized with reference to Japanese Patent Application Laid-Open No. 2010-32999.

[0157] [Dye (A3)]

The dye (A3) contains an anthraquinone dye. A well-known substance may be used for anthraquinone dye. As anthraquinone dye, for example,

C.I. Solvent Yellow 117 (hereinafter, description of C.I. Solvent Yellow, etc. will be omitted and only numbers will be described.), 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 Blue 14, 18, 35, 36, 45, 58, 59, 59:1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139,

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 Blue 1, 14, 56, 60,

C.I. direct blue 40,

C.I. Modern Red 3, 11,

C.I. modern blue 8

and the like. It is preferable that anthraquinone dye melt|dissolves in the organic solvent.

[0158] [Dye (A4)]

The dye (A4) contains a tetraazaporphyrin dye. A tetraazaporphyrin dye is a compound which has a tetraazaporphyrin skeleton in a molecule|numerator. In addition, when the tetraazaporphyrin dye is an acid dye or a basic dye, you may form the salt with arbitrary cations or anions.

[0159] The content of the colorant (A) in the colored curable resin composition is preferably 5 mass% or more and 70 mass% or less, more preferably 5 mass% or more, with respect to the total amount of solid content in the colored curable resin composition. It is 60 mass % or less, More preferably, they are 5 mass % or more and 50 mass % or less. If the content rate of a coloring agent (A) is in said range, desired spectroscopy and color density can be obtained.

[0160] In the present specification, "the total amount of solid content in the colored curable resin composition" refers to the total amount of components excluding the solvent (E) from the colored curable resin composition. The total amount of solid content and content of each component with respect to this can be measured, for example by well-known analytical means, such as liquid chromatography or gas chromatography.

[0161] The colorant (A) preferably contains at least one selected from the group consisting of the pigment and dyes (A1) to (A4).

When the colorant (A) contains the dye (A1), the colorant (A) can be contained as a dispersion in which the dye (A1) is dispersed in a solvent.

Further, in another embodiment, the colorant (A) preferably comprises a pigment and a xanthene dye (A2), more preferably 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 a pigment and a compound represented by the formula (3a), particularly more preferably a pigment and a compound represented by the formula (1-32) At least one selected from the group consisting of the compound represented by the compound, the compound represented by the formula (1-44), and the compound represented by the formula (1-97) is included.

[0162] When the colorant (A) contains the dye (A1), the content of the dye (A1) in the colorant (A) is preferably 0.5% by mass or more and 100% by mass or less, more preferably 61 They are mass % or more and 99.5 mass % or less, More preferably, they are 81 mass % or more and 99 mass % or less.

[0163] When the colorant (A) contains the dye (A2), the content of the dye (A2) in the colorant (A) is preferably 0.1 mass% or more and 80 mass% or less, more preferably 0.3 They are mass % or more and 40 mass % or less, More preferably, they are 0.5 mass % or more and 20 mass % or less.

When the colorant (A) contains the dye (A1) and the dye (A2), the mass ratio [(A1): (A2)] of the dye (A1) to the dye (A2) in the colorant (A) is, for example, 0.01 : 99.99-99.99:0.01 may be sufficient, Preferably it is 50:50-99.95:0.05, More preferably, it is 90:10-99.9:0.1.

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 it is 5:95-50:50, More preferably, it is 10:90-30:70.

[0164] When the colored curable resin composition contains a solvent (hereinafter also referred to as solvent (E)), after preparing a colorant-containing liquid containing the colorant (A) and the solvent (E) in advance, the colorant-containing liquid is You may prepare a colored curable resin composition using it. When a coloring agent (A) does not melt|dissolve in a solvent (E), a coloring agent containing liquid can be prepared as a dispersion liquid by disperse|distributing and mixing a coloring agent (A) in a solvent (E). The coloring agent containing liquid may contain a part or all of the solvent (E) contained in colored curable resin composition.

[0165] The content of solid content in the colorant-containing liquid is preferably 0.1 mass% or more and 99.9 mass% or less, more preferably 1 mass% or more and 90 mass% or less, with respect to the total amount of the colorant-containing liquid, more preferably is 1 mass % or more and 60 mass % or less, Especially preferably, they are 3 mass % or more and 50 mass % or less.

[0166] The content rate of the colorant (A) in the colorant-containing liquid is preferably 0.01 mass% or more and 100 mass% or less, more preferably 0.1 mass% or more and 99.9 mass% or less, in the total amount of solid content in the colorant-containing liquid, , More preferably, they are 1 mass % or more and 99 mass % or less, Especially preferably, they are 10 mass % or more and 90 mass % or less.

[0167] In the present specification, "total amount of solid content in the colorant-containing liquid" refers to the total amount of components excluding the solvent (E) from the colorant-containing liquid. The total amount of solid content and content of each component with respect to this can be measured by well-known analytical means, such as liquid chromatography or gas chromatography.

[0168] The colorant (A) can be uniformly dispersed in the colorant-containing liquid by subjecting the colorant (A) to a dispersion treatment containing a dispersing agent.

[0169] Examples of the dispersant include surfactants, and any surfactants selected from cationic, anionic, nonionic and amphoteric surfactants may be used. Specific examples thereof include surfactants such as polyester, polyamine, and acrylic. These dispersants may be used independently and may be used in combination of 2 or more type. As the dispersing agent, if indicated by the brand name, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Florene (manufactured by KYOEISHA CHEMICAL Co., LTD.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), EFKA (registered trademark) (manufactured by BASF Co., Ltd.), Azispa (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Inc.) and Disperbyk (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), BYK (registered trademark) ) (manufactured by BYK-Chemie Co., Ltd.) and the like.

[0170] When a dispersing agent is used to prepare the colorant-containing liquid, the amount of the dispersant (solid content) used is preferably 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the colorant (A), more Preferably they are 5 mass parts or more and 50 mass parts or less. When the usage-amount of this dispersing agent exists in the said range, there exists a tendency for the colorant containing liquid in a more uniformly dispersed state to be obtained.

[0171] [2] Resin (B)

Colored curable resin composition contains resin [henceforth resin (B)].

[0172] The resin (B) is preferably an alkali-soluble resin. Alkali solubility means the property which melt|dissolves in the developing solution which is the aqueous solution of an alkali compound. Examples of the resin (B) include the following resins [K1] to [K6].

[0173] Resin [K1]: a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides [hereinafter sometimes referred to as “monomer (a)”]; A copolymer having a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond [hereinafter sometimes referred to as “monomer (b)”).

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

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

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

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

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

[0174] The resins [K1] to [K6] may be the following copolymers or resins.

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

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

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

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

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

Resin [K6]: Resin obtained by making a monomer (a) react with the copolymer of a monomer (b) and a monomer (c), and also making carboxylic anhydride react.

[0175] Specifically, as the monomer (a),

unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene , 5-Carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclo unsaturated compounds containing a carboxy group, such as [2.2.1]hept-2-ene and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (hymic acid anhydride);

Unsaturated mono[(meth)acryl] of polyvalent carboxylic acid having more than divalence, such as succinic acid mono[2-(meth)acryloyloxyethyl] and phthalic acid mono[2-(meth)acryloyloxyethyl] royloxyalkyl]ester;

and unsaturated (meth)acrylic acid containing a hydroxyl group and a carboxyl group in the same molecule such as α-(hydroxymethyl)(meth)acrylic acid.

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

[0176] In addition, in this specification, "(meth)acryl" refers to at least one selected from the group consisting of acryl and methacryl. The same applies to descriptions such as “(meth)acryloyl” and “(meth)acrylate”.

[0177] Monomer (b) is a cyclic ether structure having 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring)) and ethylene It refers to a polymerizable compound having a sexually 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.

As the monomer (b), a monomer having an oxiranyl group and an ethylenically unsaturated bond [hereinafter, sometimes referred to as "monomer (b1)"], a monomer having an oxetanyl group and an ethylenically unsaturated bond [hereinafter referred to as "monomer (b2)" )", a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (b3)"), etc. are mentioned.

[0178] As the monomer (b1), a monomer having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon [hereinafter referred to as “monomer (b1-1)” in some cases], having a structure obtained by epoxidizing an unsaturated alicyclic hydrocarbon and monomers [hereinafter sometimes referred to as “monomer (b1-2)”].

[0179] As the monomer (b1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzylglycidyl ether Diyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis( Glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxy) Methyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) Styrene etc. are mentioned.

[0180] As the monomer (b1-2), vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (eg, Seroxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclo Hexylmethyl (meth) acrylate (eg, cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (eg, cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.) ), the compound represented by Formula (I), the compound represented by Formula (II), etc. are mentioned.

[0181]

[0182] In formulas (I) and (II), R ^aa and R ^ab each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group it may be X ^a1 and X ^a2 each independently represent a single bond, *-R ^ac -, *-R ^ac -O-, *-R ^ac -S-, or *-R ^ac -NH-. R ^ac represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond with O.

[0183] Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, and the like.

Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, and 1-hydroxy group. and a 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 ^aa and R ^ab are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group constituting R ^ac include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group. diyl, a hexane-1,6-diyl group, etc. are mentioned.

[0184] X ^a1 and X ^a2 are preferably a single bond, a methylene group, an ethylene group, a *-CH ₂ -O- group (* represents a bond with O), *-CH ₂ CH ₂ -O- group, more preferably a single bond, *-CH ₂ CH ₂ -O- group.

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

[0185]

[0186]

[0187] Specific examples of the compound represented by formula (II) include compounds represented by formulas (II-1) to (II-15), preferably formula (II-1), formula (II) -3), a compound represented by a formula (II-5), a formula (II-7), a formula (II-9), a formula (II-11) - a formula (II-15) are mentioned, More preferably The compound represented by Formula (II-1), Formula (II-7), Formula (II-9), and Formula (II-15) is mentioned.

[0188]

[0189]

[0190] The compound represented by the formula (I) and the compound represented by the formula (II) can be used independently, respectively. These can be mixed in arbitrary ratios. When mixing, the mixing ratio is Formula (I):Formula (II) [molar ratio], It is preferable that it is 5:95-95:5, It is more preferable that it is 10:90-90:10, It is 20: It is more preferable that it is 80-80:20.

[0191] The monomer (b2) is preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group.

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

The monomer (b3) is preferably a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group. As a preferable example of a monomer (b3), tetrahydrofurfuryl acrylate (For example, Viscoat V#150, OSAKA ORGANIC CHEMICAL INDUSTRY LTD make), tetrahydrofurfuryl methacrylate, etc. are mentioned.

[0192] As a specific example of the monomer (c),

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) acrylic rate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl(meth)acrylate [in the technical field, it is called "dicyclofentanyl(meth)acrylate" as a common name. Also, sometimes referred to as “tricyclodecyl (meth)acrylate.”], tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate [in the technical field, as a common name, “ Dicyclopentenyl (meth) acrylate.], dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylic (meth)acrylic acid esters such as late, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

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

Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybi Cyclo[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-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept- 2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methyl Bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxy Cycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexylox bicyclo unsaturated compounds such as cycarbonyl)bicyclo[2.2.1]hept-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl- dicarbonylimide derivatives such as 6-maleimide caproate, N-succinimidyl-3-maleimide propionate, and N-(9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among them, from the viewpoint of copolymerization reactivity and heat resistance, as (c), benzyl (meth)acrylate, tricyclodecyl (meth)acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N -benzylmaleimide, bicyclo[2.2.1]hept-2-ene, etc. are preferable. Moreover, as (c), benzyl (meth)acrylate and tricyclodecyl (meth)acrylate are more preferable at the point which is excellent in the developability at the time of pattern formation.

[0193] In the resin [K1], the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K1].

a structural unit derived from the monomer (a); Preferably 2 mol% or more and 50 mol% or less (more preferably 10 mol% or more and 45 mol% or less),

a structural unit derived from the monomer (b), particularly a structural unit derived from the monomer (b1); Preferably 50 mol% or more and 98 mol% or less (More preferably 55 mol% or more and 90 mol% or less).

When the ratio of the structural unit of resin [K1] exists in said range, there exists a tendency excellent in storage stability, developability, and solvent resistance of the pattern obtained.

[0194] Resin [K1] is the method described in the document "Experimental Method of Polymer Synthesis" (published by Takayuki Otsu, Kagaku-Dojin Publishing Company, INC. 1st Edition, 1st Edition, published on March 1, 1972) and It can be prepared with reference to the cited literature described in the relevant document.

[0195] Specifically, a predetermined amount of the monomer (a) and the monomer (b) (especially the monomer (b1)), a polymerization initiator, a solvent, etc. are placed in a reaction vessel, and stirred, heated, There are ways to keep warm. In addition, the polymerization initiator, solvent, etc. used here are not specifically limited, Any of those normally used in the said field|area can be used. Examples of the polymerization initiator include azo compounds (such as 2,2'-azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile)) and organic peroxides (such as benzoyl peroxide). there is. As a solvent, what is necessary is just to melt|dissolve each monomer, The solvent (E) etc. which are mentioned later can be used as a solvent of colored curable resin composition.

[0196] The obtained copolymer may be used as it is, a solution after the reaction, a concentrated or diluted solution, or extracted as a solid (powder) by a method such as re-precipitation. you can use that In particular, by using the below-mentioned solvent (E) as a solvent at the time of this polymerization, the solution after reaction can be used as it is, and a manufacturing process can be simplified.

[0197] In the resin [K2], the proportion of structural units derived from each is preferably in the following range among all the structural units constituting the resin [K2].

a structural unit derived from the monomer (a); Preferably 4 mol% or more and 45 mol% or less (more preferably 10 mol% or more and 30 mol% or less),

a structural unit derived from the monomer (b), particularly a structural unit derived from the monomer (b1); Preferably 2 mol% or more and 95 mol% or less (more preferably 5 mol% or more and 80 mol% or less),

a structural unit derived from the monomer (c); Preferably 1 mol% or more and 65 mol% or less (More preferably 5 mol% or more and 60 mol% or less).

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

[0198] Resin [K2] can be produced in the same manner as described for the production method of resin [K1]. Specifically, a predetermined amount of the monomer (a), the monomer (b) (especially the monomer (b1)) and the monomer (c), a polymerization initiator and a solvent are placed in a reaction vessel, and stirred, heated, and kept warm under a deoxidized atmosphere. method can be found. The obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was extracted as solid (powder) by methods, such as reprecipitation.

[0199] In the resin [K3], the proportion of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K3].

a structural unit derived from the monomer (a); Preferably 2 mol% or more and 55 mol% or less (more preferably 10 mol% or more and 50 mol% or less),

a structural unit derived from the monomer (c); Preferably 45 mol% or more and 98 mol% or less (More preferably 50 mol% or more and 90 mol% or less).

Resin [K3] can be manufactured by carrying out similarly to the method described as a manufacturing method of resin [K1].

[0200] Resin [K4] obtains a copolymer of a monomer (a) and a monomer (c), and has a cyclic ether structure having 2 to 4 carbon atoms in the monomer (b), particularly an oxirane ring in the monomer (b1) can be prepared by adding to the carboxylic acid and/or carboxylic acid anhydride of the monomer (a). Specifically, first, a copolymer of the monomer (a) and the monomer (c) is prepared in the same manner as described as the method for producing the resin [K1]. In this case, it is preferable that the ratio of the structural unit derived from each exists in the following range among all the structural units which comprise the copolymer of a monomer (a) and a monomer (c).

a structural unit derived from the monomer (a); Preferably 5 mol% or more and 50 mol% or less (more preferably 10 mol% or more and 45 mol% or less),

a structural unit derived from the monomer (c); Preferably 50 mol% or more and 95 mol% or less (More preferably 55 mol% or more and 90 mol% or less).

[0201] Next, in a part of the carboxylic acid and/or carboxylic acid anhydride derived from the monomer (a) in the copolymer, a cyclic ether structure having 2 to 4 carbon atoms in the monomer (b), particularly the monomer ( The oxirane ring of b1) is reacted. Specifically, following preparation of the copolymer of the monomer (a) and the monomer (c), the atmosphere in the flask is substituted with air from nitrogen, and the monomer (b) (particularly the monomer (b1)), carboxylic acid or carboxyl A reaction catalyst (such as tris(dimethylaminomethyl)phenol) and a polymerization inhibitor (such as hydroquinone) of an acid anhydride and a cyclic ether structure are placed in a flask, and reacted at 60 to 130°C for 1 to 10 hours By doing so, resin [K4] can be obtained.

[0202] The amount of the monomer (b), particularly the amount of the monomer (b1) used, is preferably 5 moles or more and 80 moles or less, more preferably 10 moles or more and 75 moles or less, with respect to 100 moles of the monomer (a). By setting it as this range, there exists a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and a sensitivity to become favorable. Since the reactivity of the cyclic ether structure is high and the unreacted monomer (b) hardly remains, as the monomer (b) used for the resin [K4], the monomer (b1) is preferable, and the monomer (b1-1) ) is more preferable.

[0203] The amount of the reaction catalyst used is preferably 0.001 mass % or more and 5 mass % or less with respect to the total amount of the monomer (a), the monomer (b) (particularly the monomer (b1)) and the monomer (c). It is preferable that the usage-amount of the said polymerization inhibitor is 0.001 mass % or more and 5 mass % or less with respect to the total amount of a monomer (a), a monomer (b), and a monomer (c).

Reaction conditions, such as a preparation method, reaction temperature, and time, can be suitably adjusted in consideration of manufacturing equipment, the amount of heat generated by polymerization, and the like. In addition, similarly to polymerization conditions, the preparation method and reaction temperature can be adjusted suitably in consideration of manufacturing equipment, the calorific value by polymerization, etc.

[0204] Resin [K5] is a first step, in the same manner as for the production of resin [K1], to obtain a copolymer of monomer (b) (particularly monomer (b1)) and monomer (c). As for the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, and what was extracted as a solid (powder) by methods, such as reprecipitation, may be used.

The ratio of the structural units derived from the monomer (b) (especially the monomer (b1)) and the monomer (c) is preferably in the following range with respect to the total number of moles of all the structural units constituting the copolymer.

a structural unit derived from the monomer (b), particularly a structural unit derived from the monomer (b1); Preferably 5 mol% or more and 95 mol% or less (more preferably 10 mol% or more and 90 mol% or less),

a structural unit derived from the monomer (c); Preferably 5 mol% or more and 95 mol% or less (More preferably 10 mol% or more and 90 mol% or less).

[0205] In addition, under the same conditions as in the production method of the resin [K4], the cyclic ether structure derived from the monomer (b) of the copolymer of the monomer (b) (especially the monomer (b1)) and the monomer (c) has , Resin [K5] can be obtained by reacting the carboxylic acid or carboxylic acid anhydride of the monomer (a). It is preferable that the usage-amount of the monomer (a) made to react with said copolymer is 5 mol or more and 80 mol or less with respect to 100 mol of monomer (b) (especially monomer (b1)). Since the reactivity of the cyclic ether structure is high and unreacted monomer (b) hardly remains, as the monomer (b) used for the resin [K5], the monomer (b1) is preferable, and the monomer (b1-1) is more desirable.

[0206] The resin [K6] is a resin in which the resin [K5] is further reacted with a carboxylic acid anhydride. A carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction between the cyclic ether structure and the carboxylic acid or carboxylic acid anhydride.

[0207] As the carboxylic acid anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2 and 3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (hymic acid anhydride), and the like.

[0208] Among the resins [K1] to [K6], a preferable resin as the resin (B) is [K1] or [K2]. Resin (B) may consist of 1 type of resin, and may contain 2 or more types of resin.

[0209] The weight average molecular weight (Mw) in terms of polystyrene of the resin (B) is preferably 3,000 or more and 100,000 or less, more preferably 5,000 or more and 50,000 or less, and still more preferably 5,000 or more and 30,000 or less. When a weight average molecular weight (Mw) exists in said range, the solubility with respect to the developing solution of an unexposed part is high, and there exists a tendency for the remaining-film rate and hardness of the pattern obtained also to be high. The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of resin (B) becomes like this. Preferably it is 1.1-6, More preferably, it is 1.2-4.

[0210] The acid value in terms of solid content of the resin (B) is preferably 5 mg-KOH/g or more and 200 mg-KOH/g or less, more preferably 50 mg-KOH/g or more and 180 mg-KOH/g or less, More preferably, they are 60 mg-KOH/g or more and 140 mg-KOH/g or less. An acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin, For example, it can obtain|require by titration using potassium hydroxide aqueous solution.

[0211] The content of the resin (B) in the solid content of the colored curable resin composition is preferably 1% by mass or more and 65% by mass or less, more preferably 3% by mass or more and 60% by mass or less, still more preferably They are 5 mass % or more and 55 mass % or less. When the content rate of resin (B) exists in said range, a colored pattern can be formed, and there exists a tendency for the resolution and residual film rate of a coloring pattern to improve.

[0212] In the case of preparing a colored curable resin composition using the colorant-containing liquid after preparing the colorant-containing liquid in advance, the colorant-containing liquid is a part or all of the resin (B) to be described later contained in the colored curable resin composition, Preferably, a part may be included in advance. By including the resin (B) in advance, the dispersion stability of the colorant-containing liquid can be further improved. Preferably, the colorant-containing liquid contains resin (B2) in advance.

[0213] 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 with respect to 100 parts by mass of the colorant (A). and more preferably 1 part by mass or more and 500 parts by mass or less, particularly preferably 5 parts by mass or more and 200 parts by mass or less, and still more preferably 10 parts by mass or more and 100 parts by mass or less.

[0214] [3] Polymeric compound (C)

The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by active radicals generated from the polymerization initiator (D) by light irradiation or the like, and a compound having a polymerizable ethylenically unsaturated bond (preferably ( meth)acrylic acid ester compound) and the like. It is preferable that it is 3,000 or less, and, as for the weight average molecular weight of a polymeric compound (C), it is more preferable that it is 1,500 or less. In addition, 50 or more may be sufficient as the lower limit of the weight average molecular weight of a polymeric compound (C), and 150 or more may be sufficient as it.

[0215] Among them, the polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate , pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta ( Meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaeryth Ritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, capro Lactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc. are mentioned. Especially, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are preferable.

[0216] The colored curable resin composition of the present invention may contain one or more polymerizable compounds (C). To [ content of a polymeric compound (C) ] 100 mass parts of resin (B) in colored curable resin composition, Preferably they are 20 mass parts or more and 150 mass parts or less, More preferably, they are 40 mass parts or more and 110 mass parts or less. am.

[0217] The content of the polymerizable compound (C) is preferably 1% by mass or more and 65% by mass or less, more preferably 3% by mass or more and 60% by mass or less, and still more preferably 5% by mass with respect to the total amount of solid content. They are mass % or more and 55 mass % or less. When the content rate of a polymeric compound (C) exists in said range, there exists a tendency for the residual-film rate at the time of coloring pattern formation and the chemical-resistance of a color filter to improve.

[0218] [4] polymerization initiator (D)

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating active radicals, acids, etc. under the action of light or heat, and a known polymerization initiator can be used.

[0219] Examples of the polymerization initiator (D) include oxime compounds such as O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.

[0220] The polymerization initiator (D) may be used in combination of two or more in consideration of sensitivity, formation of a precise pattern shape, and the like. Since a polymerization initiator (D) is advantageous in making precisely the pattern shape which has a sensitivity and a desired line|wire width, it is preferable to contain oxime type compounds, such as an O-acyl oxime compound.

[0221] The O-acyloxime compound is a compound having a structure represented by formula (d). Hereinafter, * represents a bond.

[0222]

[0223] Examples of the O-acyloxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl) ) Octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9 -Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-a2-methyl-4-(3) ,3-Dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl｝-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2) -Methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]-3-cyclopentylpropan-1-one-2-imine and the like, and among them, the O-acyloxime compound is N-benzoyloxy-1-(4-phenylsulfanylphenyl) Butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl) At least one selected from the group consisting of -3-cyclopentylpropan-1-one-2-imine is preferable. You may use commercial items, such as Irgacure OXE01, OXE02, OXE03 (above, BASF Corporation make), and N-1919 (made by ADEKA CORPORATION). If it is these O-acyl oxime compounds, there exists a tendency for the color filter excellent in photolithographic performance to be obtained.

[0224] The alkylphenone compound is a compound having a structure represented by formula (d4) or a structure represented by formula (d5). * represents a bond. Among these structures, the benzene ring may have a substituent.

[0225]

[0226] Examples of the compound having a structure represented by formula (d4) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-( 4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane -1-one and the like. You may use commercial items, such as Irgacure 369, 907, 379 (above, BASF Co., Ltd. product).

Examples of the compound having a structure represented by formula (d5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl) Ethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α -diethoxyacetophenone, benzyl dimethyl ketal, etc. are mentioned.

From a viewpoint of a sensitivity, as an alkylphenone compound, the compound which has a structure represented by Formula (d4) is preferable.

[0227] As the biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro Phenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Application Laid-Open Nos. H06-75372, H06-75373, etc.), 2,2'-bis( 2-Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) Biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)- 4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, Japanese Patent Publication Nos. S48-38403 and S62-174204), 4,4', and a biimidazole compound in which the phenyl group at the 5,5'-position is substituted with a carboalkoxy group (see, for example, Japanese Patent Laid-Open No. H07-10913, etc.) and the like. Among them, the compound represented by the following formula or a mixture thereof is preferable.

[0228]

[0229] As the triazine compound, 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)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl )-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine etc. are mentioned.

[0230] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Moreover, as a polymerization initiator (D), Benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, benzophenone compounds such as 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc. are mentioned. It is preferable to use these in combination with the polymerization initiation adjuvant (D1) (particularly an amine) mentioned later.

[0231] The content of the polymerization initiator (D) is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 2 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is more than part and 20 mass parts or less. When content of a polymerization initiator (D) exists in said range, since there exists a tendency for it to become highly sensitive and exposure time to shorten, there exists a tendency for productivity of a color filter to improve.

[0232] [5] polymerization initiation aid (D1)

The polymerization initiation adjuvant (D1) is a compound or sensitizer used in order to accelerate|stimulate the polymerization of the polymeric compound which superposition|polymerization was started by a polymerization initiator. When a polymerization initiator auxiliary (D1) is included, it is used in combination with a polymerization initiator (D).

Examples of the polymerization initiation auxiliary (D1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound. Especially, a thioxanthone compound is preferable. You may use together 2 or more types of polymerization initiation adjuvant (D1).

[0233] As the amine compound, triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylamino methyl benzoate, 4-dimethylamino ethyl benzoate, 4-dimethylamino benzoate isoamyl, benzoate 2-dimethylaminoethyl, 4 -Dimethylaminobenzoate 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone etc. are mentioned, Especially, 4,4'-bis(diethylamino)benzophenone is preferable. You may use commercial items, such as EAB-F (made by HODOGAYA CHEMICAL CO., LTD.).

[0234] Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9, 10-dibutoxy anthracene, 2-ethyl-9, 10- dibutoxy anthracene, etc. are mentioned.

[0235] As the thioxanthone compound, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- Propoxythioxanthone etc. are mentioned.

[0236] As the carboxylic acid compound, phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanyl Acetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

[0237] The content of the polymerization initiation auxiliary (D1) is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 1 part by mass to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is 20 mass parts or more and 20 mass parts or less. When content of a polymerization initiation adjuvant (D1) exists in said range, a blue pattern can be formed more highly sensitively, and there exists a tendency for productivity of a color filter to improve.

[0238] [6] Solvent (E)

The colored curable resin composition of this invention contains a solvent (it is also mentioned a 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.

[0239] Examples of the alkanediol diacetate having 4 to 6 carbon atoms include butanediol diacetate (also referred to as butylene glycol diacetate), pentanediol diacetate, and hexanediol diacetate. Examples of the butanediol diacetate include 1,2-butanediol diacetate, 1,3-butanediol diacetate, 1,4-butanediol diacetate, and 2,3-butanediol diacetate, preferably 1,3-butanediol diacetate. acetate and 1,4-butanediol diacetate, particularly preferably 1,4-butanediol diacetate.

[0240] The content of the alkanediol diacetate having 4 to 6 carbon atoms is 1% by mass or more and 20% by mass or less in 100% by mass of the solvent, preferably 1.5% by mass or more and 18% by mass or less, more preferably They are 2 mass % or more and 16 mass % or less, More preferably, they are 2.5 mass % or more and 14 mass % or less. If it is such a range, even after apply|coating colored curable resin composition to a board|substrate, fixed fluidity|liquidity can be ensured and it becomes possible to reduce the loading amount of a colored coating film. When the content rate of the C4-C6 alkanediol diacetate is too high, there exists a tendency for hardening of colored curable resin composition to become inadequate. Therefore, in the image development process in the manufacturing method of a color filter mentioned later, since a pattern melt|dissolves all or part in a developing solution, a desired colored coating film or a coloring pattern may not be obtained.

[0241] The alkanediol diacetate may be a high boiling point solvent, and the boiling point of the alkanediol diacetate is preferably greater than 150° C. and less than or equal to 300° C., more preferably greater than 160° C., still more preferably is 170°C or higher, still more preferably 180°C or higher, particularly preferably 190°C or higher.

[0242] Examples of the alkyl ester having 2 to 4 carbon atoms of acetic acid include ethyl acetate, propyl acetate, n-butyl acetate, and isobutyl acetate.

Especially, as for the C2-C4 alkylester of acetic acid, it is more preferable that they are n-butyl acetate and isobutyl acetate, and it is especially preferable that they are n-butyl acetate.

[0243] The content of the alkyl ester having 2 to 4 carbon atoms of acetic acid in 100 mass% of the solvent is preferably 1 mass% or more and 97 mass% or less, more preferably 2 mass% or more and 95 mass% or less, and further Preferably they are 3 mass % or more and 93 mass % or less, More preferably, they are 5 mass % or more and 90 mass % or less. 45 mass % or more, 50 mass % or more, or 60 mass % or more may be sufficient as content rate of the C2-C4 alkylester of acetic acid in 100 mass % of solvent.

[0244] The content ratio of the alkanediol diacetate having 4 to 6 carbon atoms/the alkyl ester having 2 to 4 carbon atoms of acetic acid is preferably 0.02 or more and 1.0 or less, more preferably 0.03 or more and 0.8 or less, and still more preferably 0.04 It is more than 0.7, More preferably, it is 0.05 or more and 0.5 or less. If it is such a range, even if the coloring agent density|concentration in colored curable resin composition becomes high, the loading amount of a colored coating film can be reduced.

[0245] The solvent preferably further includes an ether ester solvent having a boiling point of 150° C. or less, as will be described later.

[0246] The solvent (E) may contain the following solvents as other solvents. As another solvent (E), ester solvent (solvent containing -COO-), ether solvent other than ester solvent (solvent containing -O-), ether ester solvent (solvent containing -COO- and -O-) ), ketone solvents other than ester solvents (solvents containing -CO-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

[0247] As the ester solvent, methyl lactate, ethyl lactate, butyl lactate, 2-hydroxyisobutanoate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, and propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.

As the ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol and methylanisole and the like.

[0248] As an ether ester solvent, methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-E Methyl oxypropionate, 3-ethoxy ethyl propionate, 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-methoxypropyl propionate, 2-ethoxy methyl propionate, 2-ethoxy ethyl propionate, 2-methoxy -2-methylpropionate, 2-ethoxy-2-methylpropionate ethyl, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; Propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, etc. are mentioned.

It is preferable that they are propylene glycol monomethyl ether acetate and ethylene glycol monomethyl ether acetate, and, as for the ether ester solvent whose boiling point is 150 degrees C or less, it is especially preferable that they are propylene glycol monomethyl ether acetate.

[0249] As a ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentane on, cyclopentanone, cyclohexanone, isophorone, and the like.

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

[0251] The content of the other solvent (E) (preferably an ether ester solvent, more preferably propylene glycol monomethyl ether acetate) is 100% by mass of the solvent (E), preferably 1% by mass or more and 80% by mass Hereinafter, more preferably, they are 1 mass % or more and 70 mass % or less, More preferably, they are 2 mass % or more and 60 mass % or less, More preferably, they are 50 mass % or less or 40 mass % or less.

[0252] The content of the solvent (E) in the colored curable resin composition is preferably 70% by mass or more and 95% by mass or less, and more preferably 75% by mass or more and 92% by mass or less. In other words, solid content of colored curable resin composition becomes like this. Preferably they are 5 mass % or more and 30 mass % or less, More preferably, they are 8 mass % or more and 25 mass % or less. When content of a solvent (E) exists in said range, since the flatness at the time of application|coating becomes favorable and color density does not run short when a color filter is formed, there exists a tendency for a display characteristic to become favorable.

[0253] [7] Leveling agent (F)

The colored curable resin composition of this invention can contain 1 type, or 2 or more types of leveling agents (F). As a leveling agent (F), the silicone type surfactant (which does not have a fluorine atom), a fluorine type surfactant, and the silicone type surfactant which has a fluorine atom, etc. are mentioned. These may have a polymerizable group in a side chain.

[0254] Examples of the silicone-based 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 Co., Ltd.), KP321 , KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan LLC) and the like.

[0255] Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Limited), Megapac (registered trademark) F142D, Megapac F171, Megapac F172, Megapac F173, Megapac F177, Megapac F183, Megapac F554, Megapac R30, Megapac RS-718-K (manufactured by DIC CORPORATION), eftop (registered trademark) EF301, eftop EF303, eftop EF351, eftop EF352 (Mitsubishi Materials Electronic Chemicals Co., Ltd. manufacture), Sufflon (trademark) S381, Sufflon S382, Sufflon SC101, Sufflon SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Genkyusho), and the like.

[0256] Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include Megapac (registered trademark) R08, Megapac BL20, Megapac F475, Megapac F477, and Megapac F443 (manufactured by DIC CORPORATION).

[0257] The content of the leveling agent (F) in the colored curable resin composition is usually 0.001 mass% or more and 0.6 mass% or less, preferably 0.002 mass% or more and 0.4 mass% or less, and more preferably 0.005 mass% or more. It is 0.3 mass % or less. In addition, content of the said pigment dispersant is not contained in this content.

[0258] [8] Other ingredients

In the colored curable resin composition of the present invention, if necessary, additives such as a filler, a polymer compound other than the resin (B), an adhesion promoter, a UV absorber, an antioxidant, an aggregation inhibitor, an organic acid, an organic amine compound, a curing agent, or the like It may contain 2 or more types.

[0259] <Method for producing colored curable resin composition>

The colored curable resin composition of this invention is a coloring agent (A), resin (B), a polymeric compound (C), a polymerization initiator (D), and a solvent (E), and as needed, a leveling agent (F), superposition|polymerization It can prepare by mixing a start adjuvant (D1) and another component.

[0260] <Color filter, manufacturing method thereof, and display element>

The colored curable resin composition of this invention is useful as a material of 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 form the coloring pattern.

As a method of manufacturing a colored pattern from the colored curable resin composition of this invention, the photolithographic method, the inkjet method, the printing method, etc. are mentioned, Preferably the photolithographic method is mentioned. The photolithographic method is a method of applying a colored curable resin composition to a substrate, drying it, forming a colored composition layer, exposing the colored composition layer through a photomask, and developing. The photolithographic method WHEREIN: The colored coating film which is hardened|cured material of the said coloring composition layer can be formed by not using a photomask at the time of exposure and/or not developing. The colored pattern and colored coating film formed from the colored curable resin composition of this invention are the color filter of this invention. The color filter which concerns on this invention is typically used as a color pixel.

[0261] As the substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass coated with silica, a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicone, the substrate What formed a thin film of aluminum, silver, silver/copper/palladium alloy, etc. on it is used. On these board|substrates, another color filter layer, a resin layer, a transistor, a circuit, etc. may be formed. Moreover, you may use the board|substrate which performed the HMDS (1,1,1,3,3,3-hexamethyldisilazane) process on the silicon substrate.

[0262] Formation of each colored pixel by the photolithography method can be performed under a known or customary device or condition, and can be produced, for example, as follows. First, after apply|coating colored curable resin composition on a board|substrate, volatile components, such as a solvent, are removed and dried by heat-drying (pre-bake) and/or drying under reduced pressure, and a smooth coloring composition layer is obtained. Examples of the coating method include a spin coating method, a slit coating method, a slit-and-spin coating method, and the like.

[0263] The temperature in the case of heating and drying is preferably 30 to 120°C, more preferably 50 to 110°C. Moreover, as a heating time, between 10 seconds - 5 minutes is preferable, and between 30 seconds - 3 minutes are more preferable. When drying under reduced pressure, it is preferable to carry out under a pressure of 50 to 150 Pa at a temperature range of 20 to 25°C. The thickness of a coloring composition layer is not specifically limited, What is necessary is just to select suitably according to the thickness of the color filter made into the objective.

[0264] Next, the coloring composition layer is exposed through a photomask for forming a desired coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used. As a light source used for exposure, the light source which generate|occur|produces the light whose wavelength is 250-450 nm is preferable. For example, light of less than 350 nm may be cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, or 365 nm may be selectively extracted using a bandpass filter that extracts these wavelength ranges. . Specific examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.

[0265] In the exposure, since it is possible to uniformly irradiate parallel rays to the entire exposure surface and perform accurate alignment between the photomask and the substrate on which the coloring composition layer is formed, a mask aligner (proximity exposure machine) and It is preferable to use an exposure apparatus such as a stepper (reduced projection exposure machine).

[0266] A colored coating film (colored pattern) is formed on the substrate by developing the colored composition layer after exposure into contact with a developer. By image development, the unexposed part of a coloring composition layer melt|dissolves in a developing solution, and is removed.

It is preferable that a developing solution is an aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, and tetramethylammonium hydroxide, for example. The concentration in the aqueous solution of these alkaline compounds is preferably 0.01 to 10 mass%, more preferably 0.03 to 5 mass%. Moreover, the developing solution may contain surfactant.

[0267] The developing method may be any of a puddle method, a dipping method, and a spray method. In addition, you may incline a board|substrate at an arbitrary angle at the time of image development. After development, it is preferable to wash with water.

Moreover, it is preferable to post-bake to the obtained coloring pattern. As post-baking temperature, 80 degreeC or more and 250 degrees C or less are preferable, 100 degrees C or more and 250 degrees C or less are more preferable, 150 degrees C or more and 250 degrees C or less are still more preferable, 160 degreeC or more and 235 degrees C or less are still more preferable. As a post-baking time, 1 minute or more and 120 minutes or less are preferable, 2 minutes or more and 120 minutes or less are more preferable, 10 minutes or more and 60 minutes or less are still more preferable, 10 minutes or more and 30 minutes or less are still more preferable.

[0268] Since the thickness of the obtained coloring pattern affects adjacent pixels, it is preferable to be as thin as possible. In particular, in the case of a thick film, when a liquid crystal panel is manufactured, the light from the light source may leak through pixels of two or more colors, and when the panel is viewed from an angle, the vividness of the color may be lost. . Generally, it is preferable that it is 3 micrometers or less, and, as for the thickness of the coloring pattern after a post-baking, it is more preferable that it is 2.8 micrometers or less, It is still more preferable that it is 2.5 micrometers or less. Although the lower limit of the thickness of a coloring pattern is not specifically limited, Usually, it is 0.1 micrometer or more, Preferably it is 0.2 micrometer or more, 0.5 micrometer or more, or 1.0 micrometer or more may be sufficient. Since the colored curable resin composition of this invention shows the developability outstanding at the time of coloring pattern manufacture, it is excellent as a material of a color filter.

[0269] The colored coating film formed from the colored curable resin composition of the present invention is a color filter that is patterned on a substrate and partially overlaps with a black matrix, the thickness of the color filter on the substrate (b) and the black matrix on the The loading rate represented by the ratio [(a)/(b)] between the thicknesses (a) of the color filters of is 0.71 or less.

[0270] In Fig. 1, a color filter 1 is composed of a substrate 3, a black matrix 2, each colored pixel (not shown), and the like, and the loading rate is defined by the following equation.

Loading rate of color filter = [Thickness (a) of color filter on black matrix]/[Thickness (b) of color filter on substrate]

[0271] In the present specification, the loading rate may be defined as a value measured with respect to a colored coating film initially formed on a substrate.

The thickness of the color filter means 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 form an uneven shape or a tapered shape.

[0272] The loading rate expressed by the ratio [(a)/(b)] between the thickness (b) of the color filter on the substrate and the thickness (a) of the color filter on the black matrix is, for example, 0.75 or less, preferably is 0.74 or less, more preferably 0.73 or less, still more preferably 0.72 or less, still more preferably 0.71 or less, such as greater than 0, 0.01 or more, or 0.1 or more.

[0273] The color filter according to the present invention is useful as a color filter used for a display element, such as a liquid crystal display element, an organic EL element, electronic paper, and the like, and a solid-state imaging element.

[Example]

[0274] Hereinafter, the curable resin composition of the present invention will be described with reference to specific examples, but the present invention is not limited to the following examples unless the gist thereof is exceeded. Unless otherwise specified, "part" means "part by mass" and "%" means "mass %", respectively. In addition, unless otherwise specified, the reaction was carried out under a nitrogen atmosphere.

[0275] In the following, the structure of the compound was confirmed by mass spectrometry (LC; manufactured by Agilent Technologies, Inc., type 1200, MASS; manufactured by Agilent Technologies, Inc., type LC/MSD).

[0276] The polystyrene equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by GPC method under the following conditions.

Device ; HLC-8120GPC (manufactured by TOSOH CORPORATION)

column ; TSK-GELG2000HXL

column temperature; 40℃

solvent; THF

flow rate ; 1.0mL/min

Test solution (被檢液) solid content concentration; 0.001 to 0.01 mass %

injection volume ; 50 μL

detector ; RI

Calibration standards ; TSK STANDARD POLYSTYRENE

F-40, F-4, F-288, A-2500, A-500

(manufactured by TOSOH CORPORATION)

Ratio (Mw/Mn) of the polystyrene conversion weight average molecular weight and number average molecular weight obtained above was made into dispersion degree (molecular weight distribution).

[0277] The acid value in terms of the solid content of the resin was determined by titrating the solution containing the resin with an aqueous potassium hydroxide solution to obtain the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin.

[0278] Measuring method of loading rate [thickness (a) on line pattern/thickness (b) on substrate]

On a 2-inch square glass substrate (Eagle 2000; manufactured by Corning Incorporated) on which a line pattern (corresponding to the black matrix in Fig. 1) having a thickness of 2.0 μm was formed, a colored curable resin composition was applied by spin coating. . Thereafter, it was pre-baked at 100° C. for 3 minutes to form a coloring composition layer. After cooling, using an exposure machine (TME-150RSK; manufactured by TOPCON CORPORATION), in an atmospheric atmosphere, the coloring composition layer was irradiated with light at an exposure amount (365 nm standard) of 20 mJ/cm ² . The colored coating film was obtained by performing post-baking at 230 degreeC for 30 minutes in oven after light irradiation. After standing to cool, the thickness in each on the glass substrate and on the line pattern of the obtained colored coating film was measured using the thickness measuring apparatus (DEKTAK3; Japan Vacuum Engineering Co., Ltd. make). The thickness of the colored coating film on the line pattern is (a) the value obtained by subtracting the thickness of the line pattern from the thickness of the outermost surface of the colored coating film from the substrate, and the thickness of the colored coating film on the substrate is the coloration on the glass substrate. It was set as the thickness (b) of the coating film, and the loading rate was computed.

[0279] [Synthesis Example 1]

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was flowed into the flask, replaced with a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was put, and the mixture was heated to 80°C while stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-ylacrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-ylacrylic A mixed solution of 289 parts and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a solution obtained 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 maintained at 80°C for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B1)) solution having a solid content of 35.1% and a viscosity of 125 mPa·s as measured by a type B viscometer (23°C). The resulting copolymer had a weight average molecular weight (Mw) of 9.2×10 ³ , a degree of dispersion (molecular weight distribution) of 2.08, and an acid value in terms of solid content of 77 mg-KOH/g. Resin (B1) has the following structural units.

[0280]

[0281] [Preparation of dispersion]

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

(dispersion 1)

C.I. Pigment Red 291 (diketopyrrolopyrrole bromide) in 4.8 parts, C.I. 13.6 parts of Pigment Red 177, C.I. 2.1 parts of Pigment Yellow 150, 6.4 parts of an acrylic dispersing agent (solid content conversion), 7.9 parts of acrylic resin (solid content conversion), and 126.9 parts of propylene glycol monomethyl ether acetate, The dispersion liquid of 21.5% of solid content.

[0282] (dispersion 2)

C.I. Pigment Yellow 150, 0.9 parts, C.I. Pigment Green 58 5.5 parts, acrylic dispersing agent (solid content conversion) 1.2 parts, acrylic resin (solid content conversion) 2.5 parts, and 34.3 parts of propylene glycol monomethyl ether acetate are contained, The dispersion liquid of 22.7% of solid content.

[0283] (dispersion 3)

C.I. 4.3 parts of Pigment Blue 15:6, 0.5 parts of the compound represented by Formula (1-32), 1.3 parts of an acrylic dispersant (in terms of solid content), 1.0 parts of an acrylic resin (in terms of solid content), and propylene glycol monomethyl ether A dispersion having a solid content of 25.4% containing 20.9 parts of acetate.

[0284] [Examples 1 to 3, Comparative Examples 1 to 6]

[Preparation of colored curable resin composition]

Each component shown in Table 2 was mixed, and each colored curable resin composition was obtained.

· Colorant (A): Dispersions 1 to 3 (the numerical values in the table are the amount of the dispersion)

· Resin (B): Resin (B1) is used (the figures in the table are in terms of solid content)

· Polymerizable compound (C)

(C-1): Dipentaerythritol polyacrylate (A-9550 APHA; manufactured by Shin-Nakamura Chemical Co., Ltd.)

· Polymerization initiator (D):

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

· Solvent (E):

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

(E-2): 1,4-butylene glycol diacetate (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 (in terms of solid content)

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

[0285] [Table 2]

[0286] With respect to the obtained colored curable resin composition, a color filter was formed by the following method, and the evaluation was performed. A result is shown in Table 3.

[0287] <Formation of color filter (colored coating film)>

On a 2-inch square glass substrate (Eagle 2000; manufactured by Corning Incorporated) on which a line pattern having a thickness of 2.0 μm was formed, a colored curable resin composition was applied by spin coating, and then pre-baked at 100° C. for 3 minutes to color A composition layer was formed. After cooling, using an exposure machine (TME-150RSK; manufactured by TOPCON CORPORATION), in an atmospheric atmosphere, the coloring composition layer was irradiated with light at an exposure amount (365 nm standard) of 20 mJ/cm ² . The colored coating film was obtained by performing post-baking at 230 degreeC for 30 minutes in oven after light irradiation. After standing to cool, the thickness in each on the glass substrate and on the line pattern of the obtained colored coating film was measured using the thickness measuring apparatus (DEKTAK3; Japan Vacuum Engineering Co., Ltd. make). Table 3 shows the thickness and loading rate of the colored coating film.

[0288] [Table 3]

[0289] Compared with Comparative Examples 1 to 6, in Examples 1 to 3, since the loading rate is reduced, when a color filter or the like is manufactured from the colored curable resin composition of the present invention, it is expected that the yield will be improved.

[0290] The colored curable resin composition of the present invention can form a colored coating film with a reduced loading rate, and the yield of a color filter, a display device, a solid-state image sensor, etc. is improved, so it is very useful industrially.

[0291] 1: color filter
2: Black Matrix
3: substrate
a: thickness of color filter on black matrix
b: the thickness of the color filter on the substrate

Claims (8)

a colorant, a resin, a polymerizable compound, a polymerization initiator, and a solvent;
The solvent contains at least an alkanediol diacetate having 4 to 6 carbon atoms and an alkyl ester having 2 to 4 carbon atoms of acetic acid,
Content rate of said C4-C6 alkanediol diacetate is 1 mass % or more and 20 mass % or less in 100 mass % of solvent, Colored curable resin composition characterized by the above-mentioned. According to claim 1,
Colored curable resin composition whose content ratio ratio of the said C4-C6 alkanediol diacetate with respect to the said C2-C4 alkylester of acetic acid is 0.02 or more and 1.0 or less. 3. The method of claim 1 or 2,
The colored curable resin composition in which the said solvent further contains the ether ester solvent whose boiling point is 150 degrees C or less. 4. The method according to any one of claims 1 to 3,
The content rate of the said coloring agent is 10 mass % or more and 55 mass % or less in 100 mass % of solid content of colored curable resin composition, The said coloring agent consists of a red pigment, a green pigment, and a blue pigment. A colored curable resin composition comprising at least one selected from The color filter formed from the colored curable resin composition in any one of Claims 1-4. A color filter that is pattern-formed on a substrate and partially overlaps with a black matrix, wherein a ratio between the thickness (b) of the color filter on the substrate and the thickness (a) of the color filter on the black matrix [(a)/( b)] A color filter, characterized in that the loading rate (loading rate) represented by 0.71 or less. A display device comprising the color filter according to claim 5 or 6. A solid-state imaging element comprising the color filter according to claim 5 or 6.

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